U.S. patent number 10,954,334 [Application Number 16/653,018] was granted by the patent office on 2021-03-23 for curable composition for use in a high temperature lithography-based photopolymerization process and method of producing crosslinked polymers therefrom.
This patent grant is currently assigned to ALIGN TECHNOLOGY, INC.. The grantee listed for this patent is Align Technology, Inc.. Invention is credited to Yan Chen, Peter Dorfinger, Christian Gorsche, Gyorgy Harakaly, Srinivas Kaza, Markus Kury, Chunhua Li, Robert Liska, Jurgen Stampfl.
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United States Patent |
10,954,334 |
Liska , et al. |
March 23, 2021 |
Curable composition for use in a high temperature lithography-based
photopolymerization process and method of producing crosslinked
polymers therefrom
Abstract
Provided herein are curable compositions for use in a high
temperature lithography-based photopolymerization process, a method
of producing crosslinked polymers using said curable compositions,
crosslinked polymers thus produced, and orthodontic appliances
comprising the crosslinked polymers.
Inventors: |
Liska; Robert (Schleinbach,
AT), Gorsche; Christian (Vienna, AT),
Harakaly; Gyorgy (Vienna, AT), Kury; Markus
(Vienna, AT), Stampfl; Jurgen (Vienna, AT),
Dorfinger; Peter (Los Altos Hills, CA), Chen; Yan
(Cupertino, CA), Li; Chunhua (Cupertino, CA), Kaza;
Srinivas (Mountain View, CA) |
Applicant: |
Name |
City |
State |
Country |
Type |
Align Technology, Inc. |
San Jose |
CA |
US |
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Assignee: |
ALIGN TECHNOLOGY, INC. (San
Jose, CA)
|
Family
ID: |
1000005438449 |
Appl.
No.: |
16/653,018 |
Filed: |
October 15, 2019 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20200040130 A1 |
Feb 6, 2020 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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16403429 |
May 3, 2019 |
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62775756 |
Dec 5, 2018 |
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62667354 |
May 4, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61C
7/08 (20130101); C08G 18/10 (20130101); C08G
18/755 (20130101); A61C 7/10 (20130101); C08G
18/44 (20130101); C08G 18/73 (20130101); C08G
18/348 (20130101); C08G 18/3212 (20130101); C08G
18/3206 (20130101); C08J 5/00 (20130101); C08G
18/815 (20130101); C08J 2375/04 (20130101) |
Current International
Class: |
C08G
18/81 (20060101); A61C 7/00 (20060101); C08F
236/02 (20060101); B33Y 80/00 (20150101); C08G
18/73 (20060101); C08G 18/32 (20060101); C08G
18/34 (20060101); C08G 18/75 (20060101); C08G
18/10 (20060101); C08G 18/44 (20060101); A61C
7/10 (20060101); A61C 7/08 (20060101); C08J
5/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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WO-9528431 |
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Oct 1995 |
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WO |
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WO-2015075094 |
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May 2015 |
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WO |
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WO-2016078838 |
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May 2016 |
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WO |
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WO-2018032022 |
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Feb 2018 |
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WO |
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WO-2019213585 |
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Nov 2019 |
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WO |
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Other References
Selvamalar et al., "Copolymerization of 4-benzyloxycarbonylphenyl
methacrylate with glycidyl methacrylate: synthesis,
characterization, reactivity ratios and application as adhesives,"
Reactive and Functional Polymers, vol. 56, Issue 2, p. 89-101
(Year: 2003). cited by examiner .
Co-pending U.S. Appl. No. 16/403,429, filed May 3, 2019. cited by
applicant .
PCT/US2019/030683 International Search Report and Written Opinion
dated Aug. 26, 2019. 13 pages. cited by applicant .
Swetly et al.: Capabilities of Additive Manufacturing Technologies
(AMT) in the validation of the automotive cockpit.
RTejournal--Forum for Rapid Technology (1),
urn:nbn:de:0009-2-39579, 10 pages (2014). cited by applicant .
Tumbleston et al., Continuous Liquid Interface Production of 3D
Objects. Science, 347.6228 (Mar. 2015): 1349-1352. cited by
applicant .
European Patent Application No. 19172856.7 Extended European Search
Report (in German) dated Oct. 4, 2019. cited by applicant.
|
Primary Examiner: Roswell; Jessica M
Attorney, Agent or Firm: Wilson Sonsini Goodrich &
Rosati
Parent Case Text
CROSS REFERENCE
This application is a continuation application of U.S. patent
application Ser. No. 16/403,429, filed May 3, 2019, which claims
the benefit of U.S. Provisional Application No. 62/667,354, filed
May 4, 2018, and U.S. Provisional Application No. 62/775,756, filed
Dec. 5, 2018, each of which are incorporated herein by reference in
their entireties.
Claims
What is claimed is:
1. A curable composition for use in a high temperature
lithography-based photopolymerization process, said composition
comprising the following polymerizable Components A to C: Component
A being at least one oligomeric dimethacrylate according to the
following chemical formula (I), serving as a glass transition
temperature modifier: ##STR00039## wherein: each R.sub.1 and each
R.sub.2 independently represent a divalent, linear, branched or
cyclic C.sub.5-C.sub.15 aliphatic radical, with the proviso that at
least one of R.sub.1 and R.sub.2 is or comprises a C.sub.5-C.sub.6
cycloaliphatic structure; each R.sub.3 independently represents a
divalent, linear or branched C.sub.2-C.sub.4 alkyl radical; and n
is an integer from 1 to 5, with the proviso that R.sub.1, R.sub.2,
R.sub.3 and n are selected so as to result in a number average
molecular weight of the oligomeric dimethacrylate from 0.4 to 5
kDa; Component B being at least one, optionally polyether-modified,
(poly)carbonate-(poly)urethane dimethacrylate according to any one
of the following chemical formula (II), (III), (IV) or (V), serving
as a toughness modifier: ##STR00040## ##STR00041## wherein: each
R.sub.4 and each R.sub.5 independently represent a divalent,
linear, branched or cyclic C.sub.5-C.sub.15 aliphatic radical; each
R.sub.6 independently represents a divalent, linear or branched
C.sub.2-C.sub.4 alkyl radical; each R.sub.7 independently
represents a divalent, linear or branched C.sub.2-C.sub.6 alkyl
radical, or R.sub.7 is absent; each n is independently an integer
from 1 to 10; each m is independently an integer from 1 to 20; each
o is independently an integer from 5 to 50, or o is absent; and p
is an integer from 1 to 40, or p is absent, with the proviso that
R.sub.4, R.sub.5, R.sub.6, R.sub.7, n, m, o, and p are selected so
as to result in a number average molecular weight of the
(poly)carbonate-(poly)urethane dimethacrylate greater than 5 kDa,
and Component C being at least one mono- or multifunctional
methacrylate-based reactive diluent, wherein the at least one mono-
or multifunctional methacrylate-based reactive diluent is RD1,
having the following chemical formula: ##STR00042##
2. The curable composition of claim 1, wherein the amount of
Component A ranges from 20 to 50 wt %, the amount of Component B
ranges from 25 to 50 wt %, and the amount of Component C ranges
from 10 to 40 wt %, based on the total weight of the
composition.
3. The curable composition of claim 1, wherein Component A has a
number average molecular weight of 1 to 2 kDa.
4. The curable composition of claim 1, wherein Component B has a
number average molecular weight of 5 to 20 kDa.
5. The curable composition of claim 1, additionally comprising, in
admixture with said Components A, B and C, one or more further
components selected from the group consisting of polymerization
initiators, polymerization inhibitors, solvents, fillers,
antioxidants, pigments, colorants, surface modifiers, core-shell
particles, and mixtures thereof.
6. The curable composition of claim 1, additionally comprising one
or more photoinitiators.
7. The curable composition of claim 6, wherein the composition
comprises from 0.05 to 1 wt % of the one or more photoinitiators,
based on the total weight of the composition.
8. The curable composition of claim 1, further comprising an
additive selected from the group consisting of a resin, a defoamer,
and a surfactant.
9. The curable composition of claim 8, wherein the composition
comprises from 0.01 to 10 wt % of the additive, based on the total
weight of the composition.
10. The curable composition of claim 1, additionally comprising a
photoblocker.
11. The curable composition of claim 10, wherein the composition
comprises from 0.05 to 1 wt % of the photoblocker, based on the
total weight of the composition.
12. The curable composition of claim 1, wherein the composition
comprises a viscosity from 1 to 70 Pas at 110.degree. C.
13. The curable composition of claim 1, wherein the composition
comprises a viscosity less than 70 Pas at 90.degree. C.
14. A method for producing crosslinked polymers, the method
comprising: providing a curable composition comprising the
following polymerizable Components A to C: Component A being at
least one oligomeric dimethacrylate according to the following
chemical formula (I), serving as a glass transition temperature
modifier: ##STR00043## wherein: each R.sub.1 and each R.sub.2
independently represent a divalent, linear, branched or cyclic
C.sub.5-C.sub.15 aliphatic radical, with the proviso that at least
one of R.sub.1 and R.sub.2 is or comprises a C.sub.5-C.sub.6
cycloaliphatic structure, each R.sub.3 independently represents a
divalent, linear or branched C.sub.2-C.sub.4 alkyl radical; and n
is an integer from 1 to 5, with the proviso that R.sub.1, R.sub.2,
R.sub.3 and n are selected so as to result in a number average
molecular weight of the oligomeric dimethacrylate from 0.4 to 5
kDa; Component B being at least one, optionally polyether-modified,
(poly)carbonate-(poly)urethane dimethacrylate according to any one
of the following chemical formula (II), (III), (IV) or (V), serving
as a toughness modifier: ##STR00044## wherein: each R.sub.4 and
each R.sub.5 independently represent a divalent, linear, branched
or cyclic C.sub.5-C.sub.15 aliphatic radical; each R.sub.6
independently represents a divalent, linear or branched
C.sub.2-C.sub.4 alkyl radical; each R.sub.7 independently
represents a divalent, linear or branched C.sub.2-C.sub.6 alkyl
radical, or R.sub.7 is absent; each n is independently an integer
from 1 to 10; each m is independently an integer from 1 to 20; each
o is independently an integer from 5 to 50, or o is absent; and p
is an integer from 1 to 40, or p is absent, with the proviso that
R.sub.4, R.sub.5, R.sub.6, R.sub.7, n, m, o, and p are selected so
as to result in a number average molecular weight of the
(poly)carbonate-(poly)urethane dimethacrylate greater than 5 kDa,
and Component C being at least one mono- or multifunctional
methacrylate-based reactive diluent, wherein the at least one mono-
or multifunctional methacrylate-based reactive diluent is RD1,
having the following chemical formula: ##STR00045## and
polymerizing said curable composition, thereby producing said
crosslinked polymers.
15. The method of claim 14, wherein said step of polymerizing said
curable composition is carried out using a high temperature
lithography-based photopolymerization process.
16. The method of claim 14, wherein a solid or highly viscous resin
formulation comprising said curable composition and at least one
photoinitiator is heated to a predefined elevated process
temperature and is subsequently irradiated with light of a suitable
wavelength to be absorbed by the at least one photoinitiator,
thereby polymerizing and crosslinking the curable composition to
obtain said crosslinked polymer.
17. The method of claim 16, wherein said elevated process
temperature ranges from 50.degree. C. to 120.degree. C.
18. The method of claim 16, wherein said elevated process
temperature ranges from 90.degree. C. to 120.degree. C.
19. The method of claim 14, wherein said polymerizing comprises a
direct or additive manufacturing process.
20. The method of claim 14, wherein said polymerizing comprises a
3D printing process.
21. The method of claim 14, wherein the crosslinked polymers have
one or more, or all, of the following properties: a tensile modulus
greater than or equal to 100 MPa; an elongation at break greater
than or equal to 5%; a stress relaxation of greater than or equal
to 5% of the initial load; and a glass transition temperature of
greater than or equal to 90.degree. C.
22. The method of claim 14, wherein the crosslinked polymers have
one or more, or all, of the following properties: a tensile modulus
greater than or equal to 800 MPa; an elongation at break greater
than or equal to 20%; a stress relaxation of greater than or equal
to 20% of the initial load; and a glass transition temperature of
greater than or equal to 90.degree. C.
23. The method of claim 14, wherein the crosslinked polymers have
one or more, or all, of the following properties: a tensile modulus
greater than or equal to 1,000 MPa; an elongation at break greater
than or equal to 30%; a stress relaxation of greater than or equal
to 35%; and a glass transition temperature of greater than or equal
to 100.degree. C.
24. The method of claim 14, wherein the crosslinked polymers are
biocompatible.
25. A crosslinked polymer, obtained by a method comprising:
providing a curable composition comprising the following
polymerizable Components A to C: Component A being at least one
oligomeric dimethacrylate according to the following chemical
formula (I), serving as a glass transition temperature modifier:
##STR00046## wherein: each R.sub.1 and each R.sub.2 independently
represent a divalent, linear, branched or cyclic C.sub.5-C.sub.15
aliphatic radical, with the proviso that at least one of R.sub.1
and R.sub.2 is or comprises a C.sub.5-C.sub.6 cycloaliphatic
structure, each R.sub.3 independently represents a divalent, linear
or branched C.sub.2-C.sub.4 alkyl radical; and n is an integer from
1 to 5, with the proviso that R.sub.1, R.sub.2, R.sub.3 and n are
selected so as to result in a number average molecular weight of
the oligomeric dimethacrylate from 0.4 to 5 kDa; Component B being
at least one, optionally polyether-modified,
(poly)carbonate-(poly)urethane dimethacrylate according to any one
of the following chemical formula (II), (III), (IV) or (V), serving
as a toughness modifier: ##STR00047## wherein: each R.sub.4 and
each R.sub.5 independently represent a divalent, linear, branched
or cyclic C.sub.5-C.sub.15 aliphatic radical; each R.sub.6
independently represents a divalent, linear or branched
C.sub.2-C.sub.4 alkyl radical; each R.sub.7 independently
represents a divalent, linear or branched C.sub.2-C.sub.6 alkyl
radical, or R.sub.7 is absent; each n is independently an integer
from 1 to 10; each m is independently an integer from 1 to 20; each
o is independently an integer from 5 to 50, or o is absent; and p
is an integer from 1 to 40, or p is absent, with the proviso that
R.sub.4, R.sub.5, R.sub.6, R.sub.7, n, m, o, and p are selected so
as to result in a number average molecular weight of the
(poly)carbonate-(poly)urethane dimethacrylate greater than 5 kDa,
and Component C being at least one mono- or multifunctional
methacrylate-based reactive diluent, wherein the at least one mono-
or multifunctional methacrylate-based reactive diluent is RD1,
having the following chemical formula: ##STR00048## and
polymerizing said curable composition, thereby producing said
crosslinked polymer.
26. The crosslinked polymer of claim 25, having one or more, or
all, of the following properties: a tensile modulus greater than or
equal to 100 MPa; an elongation at break greater than or equal to
5%; a stress relaxation of greater than or equal to 5% of the
initial load; and a glass transition temperature of greater than or
equal to 90.degree. C.
27. The crosslinked polymer of claim 25, wherein said crosslinked
polymer is biocompatible.
28. The curable composition of claim 1, wherein the oligomeric
dimethacrylate of Component A is: ##STR00049##
29. The curable composition of claim 1, wherein Component B is
selected from a composition of Formula (II) and is represented by:
##STR00050## wherein each R independently represents: ##STR00051##
and n is an integer from 6 to 7.
Description
BACKGROUND OF THE INVENTION
Additive manufacturing (e.g., lithography-based additive
manufacturing (L-AM)) techniques include a variety of techniques to
fabricate objects, such as three-dimensional objects, out of
photopolymerizable materials. Due to cost, ease, and other various
factors, additive manufacturing techniques have long been used to
produce prototypes and functional items (e.g., through "rapid
prototyping") and to mass produce items. Many additive
manufacturing techniques involve successively adding layers of
photopolymerizable material and curing these layers by controlled
light exposure. The photopolymerizable materials often include
reactive components that are cured with light. Examples of
photopolymerizable materials compatible with additive manufacturing
include acrylates compatible with, e.g., radical polymerization and
epoxides compatible with, e.g., cationic polymerization. Example
viscosities of existing materials used for additive manufacturing
include viscosities of between 20-40 millipascals (mPas) (see I.
Gibson, D. W. Rosen, B. Stucker et al., "Additive Manufacturing
Technologies", Vol. 238, Springer Verlag (2010)).
It has conventionally proven difficult to form many medical
appliances through additive manufacturing techniques. One issue is
that existing materials used for additive manufacturing are not
biocompatible, much less appropriate for use in an intraoral
environment or other part of the human body. Another issue is that
existing materials used for additive manufacturing are often not
viscous enough to form the precise and/or customizable features
required of many appliances. Further, many current additive
manufacturing techniques have relatively low curing or reaction
temperatures, both for safety and cost concerns, which, for many
medical appliances (including dental appliances), undermines the
ability to produce a product that is stable at and/or above human
body temperature.
Yet another issue is that existing materials used for additive
manufacturing do not provide the physical, chemical, and/or
thermomechanical properties (elongation, time stress-relaxation,
modulus, durability, toughness, etc.) desired of aligners, other
dental appliances, hearing aids, and/or many medical devices (see,
for example, T. Swetly, J. Stampfl, G. Kempf, and R.-M. Hucke,
"Capabilities of Additive Manufacturing Technologies (AMT) in the
validation of the automotive cockpit", RTejournal--Forum for Rapid
Technology 2014 (1)). Existing materials used for additive
manufacturing lack many of the properties desired in medical
devices, such as the ability to impart forces, torques, moments,
and/or other movements that are accurate and consistent with a
treatment plan.
Increasing the viscosity of materials may provide better
thermomechanical properties for many applications by reducing
crosslinking, increasing the physical interactions between chains,
increasing the average weight of monomers, etc. As a result, it may
be possible to additively manufacture materials with desirable
thermomechanical properties and/or viscosities into dental and/or
medical appliances by adding heating operations to the processes.
For example, WO 2015/075094, WO 2016/078838 and WO 2018/032022 each
disclose stereolithography systems that heat layers of
photopolymerizable material that are to be cured in order to lower
the viscosity of the materials. Those techniques can make it
possible to process materials with resins with viscosities greater
than otherwise possible. Many of those techniques may also expand
the spectrum of monomers and/or oligomers used for additive
manufacturing, and may allow the use of a greater range of resin
formulations. Those techniques may also expand the range of
products obtained by curing the formulations referenced
therein.
Additive manufacturing is also an area of intense interest for
intraoral appliance manufacturing, as it may provide cost effective
production of precise intraoral devices, including aligners, palate
expanders and similar appliances. Additionally, the precise and
customizable nature of additive manufacturing may allow for
increased personalization of treatment, where unique devices are
quickly and facilely created via additive manufacturing. However,
some additive manufacturing techniques represent a variety of
issues for use in intraoral appliances. First, in order to be
safely used as an intraoral device, non-toxicity and
biocompatibility should be considered in designing additive
manufacturing techniques and chemistries. Second, intraoral
appliance manufacturing should be dimensionally precise.
Accordingly, viscosity plays an important role in the ability to
accurately manufacture precise intraoral appliance dimensions.
Third, many current additive manufacturing techniques have
relatively low curing or reaction temperatures, both for safety and
cost concerns. However, for intraoral appliances, it is important
to have a stable product at and above human body temperature.
Finally, the final product should have rigorous physical,
mechanical and chemical properties to provide adequate treatment to
patents. These properties include strength, elongation or
flexibility, modulus and other important properties for oral
applications.
SUMMARY OF THE INVENTION
Against the issues referenced herein, the present disclosure aims
to provide curable compositions for use in a high temperature
lithography-based photopolymerization processes. These curable
compositions may be used in a variety of applications, including
for the formation of medical devices and/or those items used in an
intraoral environment, e.g., intraoral devices, such as aligners,
expanders, or spacers. Additionally, the present disclosure aims to
provide a method of producing crosslinked polymers using said
curable compositions, as well as crosslinked polymers thus
produced, and orthodontic appliances comprising the crosslinked
polymers. Accordingly, this disclosure aims to provide
compositions, methods, and systems for use in a high temperature
lithography-based photopolymerization, as well as devices made from
said high temperature lithography-based photopolymerization.
This summary is provided to introduce a selection of concepts in a
simplified form that are further described below in the Detailed
Description. This summary is not intended to identify key features
of the claimed subject matter, nor is it intended to be used as an
aid in determining the scope of the claimed subject matter.
In various aspects, the present disclosure provides a curable
composition for use in a photopolymerization process, the
composition comprising: a toughness modifier, wherein the toughness
modifier is a polymerizable oligomer having a number average
molecular weight of greater than 5 kDa; and a reactive diluent,
wherein the reactive diluent is a polymerizable compound having a
molecular weight of 0.1 to 1.0 kDa and wherein the content of the
reactive diluent is such that the viscosity of the composition is 1
to 70 Pas at 110.degree. C. In certain aspects, the glass
transition temperature (T.sub.g) of the toughness modifier is less
than 0.degree. C. In some aspects, the content of the toughness
modifier is such that a crosslinked polymer prepared from the
curable composition has an elongation at break greater than or
equal to 5% when measured according to ISO 527-2 5B, optionally at
a crosshead speed of 5 mm/min.
In some aspects, the composition comprises 20 to 50 wt %, based on
the total weight of the composition, of the toughness modifier. In
certain aspects, the composition comprises 5 to 50 wt %, based on
the total weight of the composition, of the reactive diluent. In
some aspects, the composition further comprises 0.1 to 5 wt %,
based on the total weight of the composition, of a photoinitiator.
In certain aspects, the composition further comprises a glass
transition temperature (T.sub.g) modifier that has a higher glass
transition temperature than the toughness modifier and that is a
polymerizable oligomer having a number average molecular weight of
0.4 to 5 kDa. In certain aspects, the composition comprises 5 to 50
wt %, based on the total weight of the composition, of the glass
transition temperature (T.sub.g) modifier.
In some aspects, the toughness modifier is selected from a
polyolefin, a polyester, or a polyurethane. In certain aspects, the
toughness modifier comprises a urethane group. In some aspects, the
toughness modifier further comprises a carbonate group. In certain
aspects, the toughness modifier comprises at least one methacrylate
group. In some aspects, the toughness modifier is a compound of
formula (II), (III), (IV) or (V).
In certain aspects, the reactive diluent is monofunctional. In some
aspects, the reactive diluent comprises a methacrylate. In certain
aspects, the reactive diluent is selected from the group consisting
of dimethacrylates of polyglycols, hydroxybenzoic acid ester
(meth)acrylates, and mixtures thereof. In some aspects, the
reactive diluent is a cycloalkyl 2-, 3- or
4-((meth)acryloxy)benzoate. In certain aspects, the reactive
diluent is a compound of formula (VII):
##STR00001## wherein:
R.sub.8 represents optionally substituted C.sub.3-C.sub.10
cycloalkyl, optionally substituted 3- to 10-membered
heterocycloalkyl, or optionally substituted C.sub.6-C.sub.10
aryl;
R.sub.9 represents H or C.sub.1-C.sub.6 alkyl;
each R.sub.10 independently represents halo, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 alkoxy, Si(R.sub.11).sub.3, P(O)(OR.sub.12).sub.2,
or N(R.sub.13).sub.2; each R.sub.11 independently represents
C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 alkoxy;
each R.sub.12 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.6-C.sub.10 aryl;
each R.sub.13 independently represents H or C.sub.1-C.sub.6
alkyl;
X is absent, C.sub.1-C.sub.3 alkylene, 1- to 3-membered
heteroalkylene, or (CH.sub.2CH.sub.2O).sub.r;
Y is absent or C.sub.1-C.sub.6 alkylene;
q is an integer from 0 to 4; and
r is an integer from 1 to 4.
In some aspects, R.sub.8 is unsubstituted or substituted with one
or more substituents selected from the group consisting of
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.7
cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6-alkoxy-C.sub.6-C.sub.10-aryl,
--O(CO)--(C.sub.1-C.sub.6)alkyl, --COO--(C.sub.1-C.sub.6)alkyl,
.dbd.O, --F, --Cl, and --Br.
In certain aspects, the composition comprises a glass transition
temperature (T.sub.g) modifier that has a higher glass transition
temperature than the toughness modifier and that is a polymerizable
oligomer having a number average molecular weight of 0.4 to 5 kDa,
wherein the T.sub.g modifier comprises a urethane group. In certain
aspects, the composition comprises a glass transition temperature
(T.sub.g) modifier that has a higher glass transition temperature
than the toughness modifier and that is a polymerizable oligomer
having a number average molecular weight of 0.4 to 5 kDa, wherein
the T.sub.g modifier comprises at least one methacrylate group. In
some aspects, the composition comprises a glass transition
temperature (T.sub.g) modifier that has a higher glass transition
temperature than the toughness modifier and that is a polymerizable
oligomer having a number average molecular weight of 0.4 to 5 kDa,
wherein the T.sub.g modifier is a compound of formula (I).
In some aspects, the composition further comprises 0.1 to 10 wt %,
based on the total weight of the composition, of an additive. In
some aspects, the additive is selected from a resin, a defoamer and
a surfactant, or a combination thereof. In some aspects, the
composition comprises 0.3 to 3.5 wt %, based on the total weight of
the composition, of the additive. In some aspects, the composition
further comprises 0.05 to 1 wt %, based on the total weight of the
composition, of a photoblocker.
In various aspects, the present disclosure provides a crosslinked
polymer prepared from any one of the composition disclosed above.
In some aspects, the crosslinked polymer is characterized by one or
more of: a stress relaxation of greater than or equal to 5% of the
initial load; and a glass transition temperature of greater than or
equal to 90.degree. C. In certain aspects, the crosslinked polymer
is further characterized by one or more of: a tensile modulus
greater than or equal to 100 MPa; a tensile strength at yield
greater than or equal to 5 MPa; an elongation at yield greater than
or equal to 4%; an elongation at break greater than or equal to 5%;
a storage modulus greater than or equal to 300 MPa; and a stress
relaxation greater than or equal to 0.01 MPa.
In some aspects, the crosslinked polymer is characterized by a
stress relaxation of 5% to 45% of the initial load. In certain
aspects, the crosslinked polymer is characterized by a stress
relaxation of 20% to 45% of the initial load. In some aspects, the
crosslinked polymer is characterized by a glass transition
temperature of 90.degree. C. to 150.degree. C. In certain aspects,
the crosslinked polymer is characterized by a tensile modulus from
100 MPa to 2000 MPa. In some aspects, the crosslinked polymer is
characterized by a tensile modulus from 800 MPa to 2000 MPa. In
certain aspects, the crosslinked polymer is characterized by a
tensile strength at yield of 5 MPa to 85 MPa. In some aspects, the
crosslinked polymer is characterized by a tensile strength at yield
of 20 MPa to 55 MPa. In certain aspects, the crosslinked polymer is
characterized by a tensile strength at yield of 25 MPa to 55
MPa.
In certain aspects, the crosslinked polymer is characterized by an
elongation at yield of 4% to 10%. In some aspects, the crosslinked
polymer is characterized by an elongation at yield of 5% to 10%. In
certain aspects the crosslinked polymer is characterized by an
elongation at break of 5% to 250%. In some aspects, the crosslinked
polymer is characterized by an elongation at break of 20% to 250%.
In certain aspects, the crosslinked polymer is characterized by a
storage modulus of 300 MPa to 3000 MPa. In some aspects, the
crosslinked polymer is characterized by a storage modulus of 750
MPa to 3000 MPa.
In some aspects, the crosslinked polymer is characterized by a
stress relaxation of 0.01 MPa to 15 MPa. In certain aspects, the
crosslinked polymer is characterized by a stress relaxation of 2
MPa to 15 MPa.
In certain aspects, the crosslinked polymer is characterized by: a
stress relaxation of greater than or equal to 20% of the initial
load; a glass transition temperature of greater than or equal to
90.degree. C.; a tensile modulus from 800 MPa to 2000 MPa; and an
elongation at break greater than or equal to 20%.
In various aspects, the present disclosure provides a method of
producing crosslinked polymers comprising: providing the
composition disclosed above; and polymerizing said composition;
thereby producing said crosslinked polymers. In some aspects, said
step of polymerizing said composition is carried out using a high
temperature lithography-based photopolymerization process.
In certain aspects, a solid or highly viscous resin formulation
comprising said composition is heated to a predefined elevated
process temperature and is subsequently irradiated with light of a
suitable wavelength to be absorbed by the photoinitiator, thereby
polymerizing and crosslinking the composition to obtain said
crosslinked polymer. In some aspects, said elevated process
temperature ranges from 50.degree. C. to 120.degree. C.
In some aspects, said photopolymerization process is a direct or
additive manufacturing process. In certain aspects, said
photopolymerization process is a 3D printing process.
In various aspects, the present disclosure provides a method of
making an orthodontic appliance comprising a crosslinked polymer,
the method comprising: providing the composition disclosed above;
and fabricating the crosslinked polymer by a direct or additive
fabrication process. In some aspects, the composition is exposed to
light in said direct or additive fabrication process. In certain
aspects, the method further comprises an additional curing step
following fabrication of the crosslinked polymer.
In various aspects, the present disclosure provides a crosslinked
polymer for use in an orthodontic appliance, wherein the
crosslinked polymer is characterized by one or more of: a stress
relaxation of greater than or equal to 5% of the initial load; and
a glass transition temperature of greater than or equal to
90.degree. C. In certain aspects, the crosslinked polymer is
further characterized by one or more of: a tensile modulus greater
than or equal to 100 MPa; a tensile strength at yield greater than
or equal to 5 MPa; an elongation at yield greater than or equal to
4%; an elongation at break greater than or equal to 5%; a storage
modulus greater than or equal to 300 MPa; and a stress relaxation
greater than or equal to 0.01 MPa.
In some aspects, the crosslinked polymer is characterized by a
stress relaxation of 5% to 45% of the initial load. In certain
aspects, the crosslinked polymer is characterized by a stress
relaxation of 20% to 45% of the initial load. In some aspects, the
crosslinked polymer is characterized by a glass transition
temperature of 90.degree. C. to 150.degree. C. In certain aspects,
the crosslinked polymer is characterized by a tensile modulus from
100 MPa to 2000 MPa. In some aspects, the crosslinked polymer is
characterized by a tensile modulus from 800 MPa to 2000 MPa.
In certain aspects, the crosslinked polymer is characterized by a
tensile strength at yield of 5 MPa to 85 MPa. In some aspects, the
crosslinked polymer is characterized by a tensile strength at yield
of 20 MPa to 55 MPa. In certain aspects, the crosslinked polymer is
characterized by a tensile strength at yield of 25 MPa to 55
MPa.
In certain aspects, the crosslinked polymer is characterized by an
elongation at yield of 4% to 10%. In some aspects, the crosslinked
polymer is characterized by an elongation at yield of 5% to 10%. In
some aspects, the crosslinked polymer is characterized by an
elongation at break of 5% to 250%. In certain aspects, the
crosslinked polymer is characterized by an elongation at break of
20% to 250%.
In some aspects, the crosslinked polymer is characterized by a
storage modulus of 300 MPa to 3000 MPa. In certain aspects, the
crosslinked polymer is characterized by a storage modulus of 750
MPa to 3000 MPa. In some aspects, the crosslinked polymer is
characterized by a stress relaxation of 0.01 MPa to 15 MPa. In
certain aspects, the crosslinked polymer is characterized by a
stress relaxation of 2 MPa to 15 MPa.
In some aspects, the crosslinked polymer is characterized by: a
stress relaxation of greater than or equal to 20% of the initial
load; a glass transition temperature of greater than or equal to
90.degree. C.; a tensile modulus from 800 MPa to 2000 MPa; and an
elongation at break greater than or equal to 20%.
In some aspects, the crosslinked polymer comprises a first
repeating unit having a number average molecular weight of greater
than 5 kDa, wherein the first repeating unit comprises carbonate
and urethane groups. In certain aspects, the first repeating unit
is derived from a (poly)carbonate-(poly)urethane dimethacrylate
oligomer. In some aspects, the number average molecular weight of
the (poly)carbonate-(poly)urethane dimethacrylate oligomer is
between 5 kDa to 20 kDa. In some aspects, the number average
molecular weight of the (poly)carbonate-(poly)urethane
dimethacrylate oligomer is between 10 kDa to 20 kDa.
In some aspects, the crosslinked polymer comprises a second
repeating unit having a number average molecular weight of 0.4 to 5
kDa, wherein the second repeating unit comprises a urethane group.
In certain aspects, the second repeating unit is derived from a
(poly)urethane dimethacrylate oligomer. In some aspects, the
crosslinked polymer comprises a monomer of the formula:
##STR00002## wherein:
R.sub.8 represents optionally substituted C.sub.3-C.sub.10
cycloalkyl, optionally substituted 3- to 10-membered
heterocycloalkyl, or optionally substituted C.sub.6-C.sub.10
aryl;
R.sub.9 represents H or C.sub.1-C.sub.6 alkyl;
each R.sub.10 independently represents halo, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 alkoxy, Si(R.sub.u).sub.3, P(O)(OR.sub.12).sub.2,
or N(R.sub.13).sub.2;
each R.sub.11 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.1-C.sub.6 alkoxy;
each R.sub.12 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.6-C.sub.10 aryl;
each R.sub.13 independently represents H or C.sub.1-C.sub.6
alkyl;
X is absent, C.sub.1-C.sub.3 alkylene, 1- to 3-membered
heteroalkylene, or (CH.sub.2CH.sub.2O).sub.r;
Y is absent or C.sub.1-C.sub.6 alkylene;
q is an integer from 0 to 4; and
r is an integer from 1 to 4
wherein each dashed line represents a bond to a carbon atom.
In some aspects, R.sub.8 is unsubstituted or substituted with one
or more substituents selected from the group consisting of
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.7
cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6-alkoxy-C.sub.6-C.sub.10-aryl,
--O(CO)--(C.sub.1-C.sub.6)alkyl, --COO--(C.sub.1-C.sub.6)alkyl,
.dbd.O, --F, --Cl, and --Br.
In some aspects, the crosslinked polymer comprises 20 to 50 wt % of
the first repeating unit based on the total weight of the
crosslinked polymer. In certain aspects, the crosslinked polymer
comprises 25 to 50% of the first repeating unit based on the total
weight of the crosslinked polymer. In some aspects, the crosslinked
polymer comprises 1 to 50 wt % of the second repeating unit based
on the total weight of the crosslinked polymer. In certain aspects,
the crosslinked polymer comprises 20 to 50 wt % of the second
repeating unit based on the total weight of the crosslinked
polymer. In some aspects, the crosslinked polymer comprises 1 to 80
wt % of the monomer based on the total weight of the crosslinked
polymer. In certain aspects, the crosslinked polymer comprises 10
to 40 wt % of the monomer based on the total weight of the
crosslinked polymer.
In various aspects, the present disclosure provides an orthodontic
appliance comprising the crosslinked polymer described above. In
some aspects, the orthodontic appliance is an aligner, expander or
spacer. In certain aspects, the orthodontic appliance comprises a
plurality of tooth receiving cavities configured to reposition
teeth from a first configuration toward a second configuration. In
some aspects, the orthodontic appliance is one of a plurality of
orthodontic appliances configured to reposition the teeth from an
initial configuration toward a target configuration. In certain
aspects, the orthodontic appliance is one of a plurality of
orthodontic appliances configured to reposition the teeth from an
initial configuration toward a target configuration according to a
treatment plan.
In various aspects, the present disclosure provides a curable
composition for use in a high temperature lithography-based
photopolymerization process, said composition comprising the
following polymerizable Components A to C:
Component A being at least one oligomeric dimethacrylate according
to the following chemical formula (I), serving as a glass
transition temperature modifier:
##STR00003## wherein:
each R.sub.1 and each R.sub.2 independently represent a divalent,
linear, branched or cyclic C.sub.5-C.sub.15 aliphatic radical, with
the proviso that at least one of R.sub.1 and R.sub.2 is or
comprises a C.sub.5-C.sub.6 cycloaliphatic structure,
each R.sub.3 independently represents a divalent, linear or
branched C.sub.2-C.sub.4 alkyl radical, and
n is an integer from 1 to 5, with the proviso that R.sub.1,
R.sub.2, R.sub.3 and n are selected so as to result in a number
average molecular weight of the oligomeric dimethacrylate from 0.4
to 5 kDa;
Component B being at least one, optionally polyether-modified,
(poly)carbonate-(poly)urethane dimethacrylate according to any one
of the following chemical formulas (II), (III), (IV) or (V),
serving as a toughness modifier:
##STR00004## wherein:
each R.sub.4 and each R.sub.5 independently represent a divalent,
linear, branched or cyclic C.sub.5-C.sub.15 aliphatic radical,
each R.sub.6 independently represents a divalent, linear or
branched C.sub.2-C.sub.4 alkyl radical,
each R.sub.7 independently represents a divalent, linear or
branched C.sub.2-C.sub.6 alkyl radical,
each n is independently an integer from 1 to 10,
each m is independently an integer from 1 to 20,
each o is independently an integer from 5 to 50, and
p is an integer from 1 to 40,
with the proviso that R.sub.4, R.sub.5, R.sub.6, R.sub.7, n, m, o
and p are selected so as to result in a number average molecular
weight of the (poly)carbonate-(poly)urethane dimethacrylate greater
than 5 kDa; and
Component C being at least one mono- or multifunctional
methacrylate-based reactive diluent.
In some aspects, the amount of Component A ranges from 20 to 50 wt
%, the amount of Component B ranges from 25 to 50 wt %, and the
amount of Component C ranges from 10 to 40 wt %, based on the total
weight of the curable composition. In certain aspects, R.sub.1 is a
divalent radical originating from a diol selected from the group
consisting of 1,4-cyclohexanedimethanol (CHDM),
4,4'-isopropylidenedicyclohexanol (HBPA),
4,8-bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane (HTCD),
3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,
1,3-bis(hydroxymethyl)adamantane, 1,4-, 1,3- or
1,2-dihydroxycyclohexane, 1,3-adamantanediol,
4-hydroxy-.alpha.,.alpha.,4-trimethylcyclohexanemethanol,
2,3-pinanediol, 1,6-hexanediol, and mixtures thereof. In some
aspects, R.sub.1 is a divalent radical originating from
1,4-cyclohexanedimethanol (CHDM).
In certain aspects, R.sub.2 and R.sub.5 are divalent radicals
originating from a diisocyanate independently selected from the
group consisting of isophorone diisocyanate (IPDI), hexamethylene
diisocyanate (HDI), trimethylhexamethylene diisocyanate (2,2,4- and
2,4,4-mixture, TMDI), dicyclohexylmethane 4,4'-diisocyanate (HMDI),
1,3-bis(isocyanatomethyl)cyclohexane, and mixtures thereof. In some
aspects, R.sub.2 is a divalent radical originating from isophorone
diisocyanate (IPDI) or hexamethylene diisocyanate (HDI).
In some aspects, R.sub.3 and R.sub.6 are divalent radicals
originating from a diol independently selected from the group
consisting of 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol,
1,4-butanediol, and mixtures thereof. In certain aspects, R.sub.3
and R.sub.6 are divalent radicals originating from
1,2-ethanediol.
In certain aspects, R.sub.4 is a divalent radical originating from
a diol selected from the group consisting of
2,2-dimethyl-1,3-propanediol (DMP), 1,6-hexanediol,
1,4-cyclohexanedimethanol (CHDM), and mixtures thereof. In some
aspects, R.sub.4 is the alcoholic moiety of a polycarbonate.
In some aspects, R.sub.7 is a divalent radical originating from a
diol selected from the group consisting of C.sub.2-C.sub.6
alkanediols and mixtures thereof. In certain aspects, R.sub.7 is a
divalent radical originating from 1,4-butanediol.
In certain aspects, n in formula (I) is 1 or 2. In some aspects, n
in the formulas (II) to (V) ranges from 5 to 8. In certain aspects,
m in the formulas (II) to (V) ranges from 5 to 10. In certain
aspects, o in the formulas (II) to (V) ranges from 35 to 45. In
some aspects, p in the formulas (II) to (V) ranges from 2 to 5.
In some aspects, the methacrylate-based reactive diluent of
Component C is selected from the group consisting of
dimethacrylates of polyglycols, hydroxybenzoic acid ester
(meth)acrylates, and mixtures thereof. In certain aspects, the
reactive diluent is a cycloalkyl 2-, 3- or
4-((meth)acryloxy)benzoate. In some aspects, the reactive diluent
is a compound of formula (VII):
##STR00005## wherein:
R.sub.8 represents optionally substituted C.sub.3-C.sub.10
cycloalkyl, optionally substituted 3- to 10-membered
heterocycloalkyl, or optionally substituted C.sub.6-C.sub.10
aryl;
R.sub.9 represents H or C.sub.1-C.sub.6 alkyl;
each R.sub.10 independently represents halo, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 alkoxy, Si(R.sub.u).sub.3, P(O)(OR.sub.12).sub.2,
or N(R.sub.13).sub.2; each R.sub.11 independently represents
C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 alkoxy;
each R.sub.12 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.6-C.sub.10 aryl;
each R.sub.13 independently represents H or C.sub.1-C.sub.6
alkyl;
X is absent, C.sub.1-C.sub.3 alkylene, 1- to 3-membered
heteroalkylene, or (CH.sub.2CH.sub.2O).sub.r;
Y is absent or C.sub.1-C.sub.6 alkylene;
q is an integer from 0 to 4; and
r is an integer from 1 to 4.
In certain aspects, R.sub.8 is unsubstituted or substituted with
one or more substituents selected from the group consisting of
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.7
cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6-alkoxy-C.sub.6-C.sub.10-aryl,
--O(CO)--(C.sub.1-C.sub.6)alkyl, --COO--(C.sub.1-C.sub.6)alkyl,
.dbd.O, --F, --Cl, and --Br.
In some aspects, Component A has a number average molecular weight
of 1 to 2 kDa. In certain aspects, Component B has a number average
molecular weight of 5 to 20 kDa.
In certain aspects, the composition additionally comprises, in
admixture with said Components A, B and C, one or more further
components selected from the group consisting of polymerization
initiators, polymerization inhibitors, solvents, fillers,
antioxidants, pigments, colorants, surface modifiers, core-shell
particles, and mixtures thereof. In some aspects, the composition
additionally comprises one or more photoinitiators.
In various aspects, the present disclosure provides a method of
producing crosslinked polymers comprising: providing a curable
composition comprising a composition as described above; and
polymerizing said curable composition; thereby producing said
crosslinked polymers. In some aspects, said step of polymerizing
said curable composition is carried out using a high temperature
lithography-based photopolymerization process.
In certain aspects, a solid or highly viscous resin formulation
comprising said curable composition and at least one photoinitiator
is heated to a predefined elevated process temperature and is
subsequently irradiated with light of a suitable wavelength to be
absorbed by the photoinitiator, thereby polymerizing and
crosslinking the curable composition to obtain said crosslinked
polymer. In some aspects, said elevated process temperature ranges
from 50.degree. C. to 120.degree. C. In certain aspects, said
elevated process temperature ranges from 90.degree. C. to
120.degree. C. In some aspects, said photopolymerization process is
a direct or additive manufacturing process. In certain aspects,
said photopolymerization process is a 3D printing process.
In various aspects, the present disclosure provides a crosslinked
polymer, obtained by the method described above. In some aspects,
the crosslinked polymer has one or more, or all, of the following
properties: a tensile modulus greater than or equal to 100 MPa; an
elongation at break greater than or equal to 5%; a stress
relaxation of greater than or equal to 5% of the initial load; and
a glass transition temperature of greater than or equal to
90.degree. C. In certain aspects, the crosslinked polymer has one
or more, or all, of the following properties: a tensile modulus
greater than or equal to 800 MPa; an elongation at break greater
than or equal to 20%; a stress relaxation of greater than or equal
to 20% of the initial load; and a glass transition temperature of
greater than or equal to 90.degree. C. In some aspects, the
crosslinked polymer has one or more, or all, of the following
properties: a tensile modulus greater than or equal to 1,000 MPa;
an elongation at break greater than or equal to 30%; a stress
relaxation of greater than or equal to 35%; and a glass transition
temperature of greater than or equal to 100.degree. C. In certain
aspects, said crosslinked polymer is biocompatible.
In various aspects, the present disclosure provides an orthodontic
appliance comprising the crosslinked polymer described above. In
certain aspects, the orthodontic appliance is an aligner, expander
or spacer.
INCORPORATION BY REFERENCE
All publications, patents, and patent applications mentioned in
this specification are herein incorporated by reference to the same
extent as if each individual publication, patent, or patent
application was specifically and individually indicated to be
incorporated by reference.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features of the invention are set forth with
particularity in the appended claims. A better understanding of the
features and advantages of the present disclosure will be obtained
by reference to the following detailed description that sets forth
illustrative embodiments, in which the principles of the invention
are utilized, and the accompanying drawings of which:
FIG. 1A illustrates a tooth repositioning appliance, in accordance
with embodiments.
FIG. 1B illustrates a tooth repositioning system, in accordance
with embodiments.
FIG. 1C illustrates a method of orthodontic treatment using a
plurality of appliances, in accordance with embodiments.
FIG. 2 illustrates a method for designing an orthodontic appliance,
in accordance with embodiments.
FIG. 3 illustrates a method for digitally planning an orthodontic
treatment, in accordance with embodiments.
FIG. 4 shows a schematic configuration of a high temperature
additive manufacturing device used for curing a curable
compositions of the present disclosure by means of a 3D printing
process.
FIG. 5a, FIG. 5b, FIG. 5c, FIG. 5d, FIG. 5e, and FIG. 5f show the
results obtained by measuring the viscosities (Pas) of curable
compositions (1) to (10) at varying temperatures (.degree. C.).
FIG. 6a, FIG. 6b, FIG. 6c, FIG. 6d, FIG. 6e, and FIG. 6f show the
results obtained by measuring the storage moduli (GPa) of
crosslinked polymers resulting from photopolymerizing curable
compositions (1) to (10) at varying temperatures (.degree. C.).
FIG. 7a, FIG. 7b, FIG. 7c, FIG. 7d, FIG. 7e, and FIG. 7f show the
results obtained by measuring the tensile strengths (N/mm.sup.2) of
crosslinked polymers resulting from photopolymerizing curable
compositions (1) to (10) at varying strains (%).
DETAILED DESCRIPTION OF THE INVENTION
All terms, chemical names, expressions and designations have their
usual meanings which are well-known to those skilled in the art. As
used herein, the terms "to comprise" and "comprising" are to be
understood as non-limiting, i.e. other components than those
explicitly named may be included. Number ranges are to be
understood as inclusive, i.e. including the indicated lower and
upper limits.
As used herein, the term "polymer" refers to a molecule composed of
repeating structural units connected by covalent chemical bonds and
characterized by a substantial number of repeating units (e.g.,
equal to or greater than 10 repeating units and often equal to or
greater than 50 repeating units and often equal to or greater than
100 repeating units) and a high molecular weight (e.g. greater than
5,000 Da, 10,000 Da or 20,000 Da). Polymers are commonly the
polymerization product of one or more monomer precursors. The term
polymer includes homopolymers, or polymers consisting essentially
of a single repeating monomer subunit. The term polymer also
includes copolymers which are formed when two or more different
types of monomers are linked in the same polymer. Copolymers may
comprise two or more monomer subunits, and include random, block,
alternating, segmented, grafted, tapered and other copolymers.
"Crosslinked polymers" refer to polymers having one or multiple
links between at least two polymer chains, which preferably result
from multivalent monomers forming crosslinking sites upon
polymerization.
Herein, an "oligomer" refers to a molecule composed of repeating
structural units connected by covalent chemical bonds and
characterized by a number of repeating units less than that of a
polymer (e.g., equal to or less than 10 repeating units) and a
lower molecular weight than polymers (e.g. less than 5,000 Da or
2,000 Da). Oligomers may be the polymerization product of one or
more monomer precursors. In an embodiment, an oligomer or a monomer
cannot be considered a polymer in its own right.
A "prepolymer" refers to a polymer or oligomer the molecules of
which are capable of entering, through reactive groups, into
further polymerization.
Oligomers and polymer mixtures can be characterized and
differentiated from other mixtures of oligomers and polymers by
measurements of molecular weight and molecular weight
distributions.
The average molecular weight (M) is the average number of repeating
units n x the molecular weight or molar mass (Mi) of the repeating
unit. The number-average molecular weight (Mn) is the arithmetic
mean, representing the total weight of the molecules present
divided by the total number of molecules. Number average molecular
weights are typically measured by gel permeation
chromatography.
Photoinitiators that are useful in the disclosure include those
that can be activated with light and initiate polymerization of the
polymerizable components of the formulation.
Photopolymerization occurs when suitable formulations are exposed
to light of sufficient power and of a wavelength capable of
initiating polymerization. The wavelengths and power of light
useful to initiate polymerization depends on the initiator used.
Light as used herein includes any wavelength and power capable of
initiating polymerization. Preferred wavelengths of light include
ultraviolet (UV) or visible. UV light sources include UVA
(wavelength about 400 nm to about 320 nm), UVB (about 320 nm to
about 290 nm) or UVC (about 290 nm to about 100 nm). Any suitable
source may be used, including laser sources. The source may be
broadband or narrowband, or a combination thereof. The light source
may provide continuous or pulsed light during the process. Both the
length of time the system is exposed to UV light and the intensity
of the UV light can be varied to determine the ideal reaction
conditions.
Additive manufacturing includes a variety of technologies which
fabricate three-dimensional objects directly from digital models
through an additive process. In some aspects, successive layers of
material are deposited and "cured in place". A variety of
techniques are known to the art for additive manufacturing,
including selective laser sintering (SLS), fused deposition
modeling (FDM) and jetting or extrusion. In many embodiments,
selective laser sintering involves using a laser beam to
selectively melt and fuse a layer of powdered material according to
a desired cross-sectional shape in order to build up the object
geometry. In many embodiments, fused deposition modeling involves
melting and selectively depositing a thin filament of thermoplastic
polymer in a layer-by-layer manner in order to form an object. In
yet another example, 3D printing can be used to fabricate the
appliances herein. In many embodiments, 3D printing involves
jetting or extruding one or more materials onto a build surface in
order to form successive layers of the object geometry.
Photopolymers may be fabricated by "vat" processes in which light
is used to selectively cure a vat or reservoir of the photopolymer.
Each layer of photopolymer may be selectively exposed to light in a
single exposure or by scanning a beam of light across the layer.
Specific techniques include stereolithography (SLA), Digital Light
Processing (DLP) and two photon-induced photopolymerization
(TPIP).
Continuous direct fabrication methods for photopolymers have also
been reported. For example, a direct fabrication process can
achieve continuous build-up of an object geometry by continuous
movement of the build platform (e.g., along the vertical or
Z-direction) during the irradiation phase, such that the hardening
depth of the irradiated photopolymer is controlled by the movement
speed. Accordingly, continuous polymerization of material on the
build surface can be achieved. Such methods are described in U.S.
Pat. No. 7,892,474, the disclosure of which is incorporated herein
by reference in its entirety. In yet another example, a continuous
direct fabrication method utilizes a "heliolithography" approach in
which the liquid photopolymer is cured with focused radiation while
the build platform is continuously rotated and raised. Accordingly,
the object geometry can be continuously built up along a spiral
build path. Such methods are described in U.S. Patent Publication
No. 2014/0265034, the disclosure of which is incorporated herein by
reference in its entirety. Continuous liquid interface production
of 3D objects has also been reported (J. Tumbleston et al.,
Science, 2015, 347 (6228), pp 1349-1352) hereby incorporated by
reference in its entirety for description of the process. Another
example of continuous direct fabrication method can involve
extruding a composite material composed of a curable liquid
material surrounding a solid strand. The composite material can be
extruded along a continuous three-dimensional path in order to form
the object. Such methods are described in U.S. Patent Publication
No. 2014/0061974, the disclosure of which is incorporated herein by
reference in its entirety.
"Biocompatible" refers to a material that does not elicit an
immunological rejection or detrimental effect, referred herein as
an adverse immune response, when it is disposed within an in-vivo
biological environment. For example, in embodiments a biological
marker indicative of an immune response changes less than 10%, or
less than 20%, or less than 25%, or less than 40%, or less than 50%
from a baseline value when a human or animal is exposed to or in
contact with the biocompatible material. Alternatively, immune
response may be determined histologically, wherein localized immune
response is assessed by visually assessing markers, including
immune cells or markers that are involved in the immune response
pathway, in and adjacent to the material. In an aspect, a
biocompatible material or device does not observably change immune
response as determined histologically. In some embodiments, the
disclosure provides biocompatible devices configured for long-term
use, such as on the order of weeks to months, without invoking an
adverse immune response. Biological effects may be initially
evaluated by measurement of cytotoxicity, sensitization, irritation
and intracutaneous reactivity, acute systemic toxicity,
pyrogenicity, subacute/subchronic toxicity and/or implantation.
Biological tests for supplemental evaluation include testing for
chronic toxicity.
"Bioinert" refers to a material that does not elicit an immune
response from a human or animal when it is disposed within an
in-vivo biological environment. For example, a biological marker
indicative of an immune response remains substantially constant
(plus or minus 5% of a baseline value) when a human or animal is
exposed to or in contact with the bioinert material. In some
embodiments, the disclosure provides bioinert devices.
In embodiments, the crosslinked polymers are characterized by a
tensile stress-strain curve that displays a yield point after which
the test specimen continues to elongate, but there is no increase
in load. Such yield point behavior typically occurs "near" the
glass transition temperature, where the material is between the
glassy and rubbery regimes and may be characterized as having
viscoelastic behavior. In embodiments, viscoelastic behavior is
observed in the temperature range 20.degree. C. to 40.degree. C.
The yield stress is determined at the yield point. In some
embodiments, the yield point follows an elastic region in which the
slope of the stress-strain curve is constant or nearly constant. In
embodiments, the modulus is determined from the initial slope of
the stress-strain curve or as the secant modulus at 1% strain (e.g.
when there is no linear portion of the stress-strain curve). The
elongation at yield is determined from the strain at the yield
point. When the yield point occurs at a maximum in the stress, the
ultimate tensile strength is less than the yield strength. For a
tensile test specimen, the strain is defined by ln (1/10), which
may be approximated by (1-10)/10 at small strains (e.g. less than
approximately 10%) and the elongation is 1/10, where 1 is the gauge
length after some deformation has occurred and 10 is the initial
gauge length. The mechanical properties can depend on the
temperature at which they are measured. The test temperature may be
below the expected use temperature for a dental appliance such as
35.degree. C. to 40.degree. C. In embodiments, the test temperature
is 23.+-.2.degree. C.
In embodiments, the stress relaxation can be measured by monitoring
the time-dependent stress resulting from a steady strain. The
extent of stress relaxation can also depend on the temperature,
relative humidity and other applicable conditions (e.g., presence
of water). In embodiments, the test conditions for stress
relaxation are a temperature is 37.+-.2.degree. C. at 100% relative
humidity or a temperature of 37.+-.2.degree. C. in water.
The dynamic viscosity of a fluid indicates its resistance to
shearing flows. The SI unit for dynamic viscosity is the Poiseuille
(Pas). Dynamic viscosity is commonly given in units of centipoise,
where 1 centipoise (cP) is equivalent to 1 mPas. Kinematic
viscosity is the ratio of the dynamic viscosity to the density of
the fluid; the SI unit is m.sup.2/s. Devices for measuring
viscosity include viscometers and rheometers. The viscosity of a
composition described herein may be measured at 110.degree. C.
using a rheometer. For example, an MCR 301 rheometer from Anton
Paar may be used for rheological measurement in rotation mode
(PP-25, 50 s-1, 50-115.degree. C., 3.degree. C./min).
In certain aspects, the present disclosure provides a curable
composition for use in a photopolymerization process, the
composition comprising:
1 to 70 wt %, based on the total weight of the composition, of a
toughness modifier, wherein the toughness modifier is a
polymerizable oligomer having a number average molecular weight of
greater than 5 kDa;
5 to 80 wt %, based on the total weight of the composition, of a
reactive diluent, wherein the reactive diluent is a polymerizable
compound having a molecular weight of 0.1 to 1.0 kDa; and 0.1 to 5
wt %, based on the total weight of the composition, of a
photoinitiator;
wherein the viscosity of the composition is 1 to 70 Pas at
110.degree. C.
In some embodiments, the composition comprises:
20 to 50 wt %, based on the total weight of the composition, of a
toughness modifier, wherein the toughness modifier is a
polymerizable oligomer having a number average molecular weight of
greater than 10 kDa;
5 to 80 wt %, based on the total weight of the composition, of a
reactive diluent, wherein the reactive diluent is a polymerizable
compound having a molecular weight of 0.1 to 0.5 kDa; and
0.1 to 5 wt %, based on the total weight of the composition, of a
photoinitiator;
wherein the viscosity of the composition is 1 to 70 Pas at
110.degree. C.
Combining a toughness modifier and a reactive diluent to form a
composition of the present disclosure results in a curable
composition being well processible at the processing temperatures
usually employed in high temperature lithography-based
photopolymerization processes, i.e. temperatures between 90.degree.
C. and 120.degree. C., as their viscosities at these temperatures
are sufficiently low, despite the presence of the high molecular
weight toughness modifier. Moreover, as such curable compositions
typically comprise multiple divalent polymerizable components, they
result in crosslinked polymers, more specifically in crosslinked
polymers having excellent thermomechanical properties, as detailed
below.
The toughness modifier and the reactive diluent are typically
miscible and compatible in the methods described herein. When used
in the subject compositions, the toughness modifier may provide for
high elongation at break and toughness via strengthening effects,
and the reactive diluent may improve the processability of the
formulations, particularly of those comprising high amounts of
toughness modifiers, while maintaining high values for strength and
T.sub.g.
A toughness modifier of the subject compositions may have a low
glass transition temperature (T.sub.g), such as a T.sub.g less than
0.degree. C. In some examples, the T.sub.g of the toughness
modifier may be less than 25.degree. C., such as less than
15.degree. C., less than 10.degree. C., less than 5.degree. C.,
less than 0.degree. C., less than -5.degree. C., or less than
-10.degree. C. The T.sub.g of a polymer or composition described
herein may be assessed using dynamic mechanical analysis (DMA) and
is provided herein as the tan .delta. peak.
The toughness modifier can be a component having a low glass
transition temperature (e.g., below 0.degree. C.), which can add to
tough behavior if used above its glass transition temperature. The
toughness modifier can have a molecular weight greater than 5 kDa,
6 kDa, 7 kDa, 8 kDa, 9 kDa, 10 kDa, 11 kDa, 12 kDa, 13 kDa, 14 kDa,
15 kDa, 16 kDa, 17 kDa, 18 kDa, 19 kDa, 20 kDa, 21 kDa, 22 kDa, 23
kDa, 24 kDa, or greater than 25 kDa. In certain embodiments, the
toughness modifier can have a molecular weight greater than 5 kDa,
such as a molecular weight greater than 10 kDa. The curable
composition can comprise 10 to 70 wt %, 10 to 60 wt %, 10 to 50 wt
%, 10 to 40 wt %, 10 to 30 wt %, 10 to 25 wt %, 20 to 60 wt %, 20
to 50 wt %, 20 to 40 wt %, 20 to 35 wt %, 20 to 30 wt %, 25 to 60
wt %, 25 to 50 wt %, 25 to 45 wt %, 25 to 40 wt %, or 25 to 35 wt
%, based on the total weight of the composition, of the toughness
modifier. In certain embodiments, the curable composition may
comprise 25 to 35 wt %, based on the total weight of the
composition, of the toughness modifier. In certain embodiments, the
curable composition may comprise 20 to 40 wt %, based on the total
weight of the composition, of the toughness modifier.
The toughness modifier may comprise a polyolefin, a polyester, a
polyurethane, a polyvinyl, a polyamide, a polyether, a polyacrylic,
a polycarbonate, a polysulfone, a polyarylate, a cellulose-based
resin, a polyvinyl chloride resin, a polyvinylidene fluoride, a
polyvinylidene chloride, a cycloolefin-based resin, a
polybutadiene, a glycidyl methacrylate, or a methyl acrylic ester.
For example, the toughness modifier may comprise a urethane group,
a carbonate group, or both a urethane group and a carbonate
group.
In some embodiments, the toughness modifier comprises at least one
methacrylate group, such as at least two methacrylate groups. In
some embodiments, the toughness modifier comprises at least one
acrylate. The toughness modifier can be an acrylate selected from
an epoxy acrylate (e.g., a Bisphenol A epoxy acrylate), an epoxy
methacrylate (e.g., a Bisphenol A epoxy methacrylate), a novolac
type epoxy acrylate (e.g., cresol novolac epoxy acrylate or phenol
novolac epoxy acrylate), a modified epoxy acrylate (e.g., phenyl
epoxy acrylate, aliphatic alkyl epoxy acrylate, soybean oil epoxy
acrylate, Photocryl.RTM. DP296, Photocryl.RTM. E207/25TP,
Photocryl.RTM. E207/25HD, or Photocryl.RTM. E207/30PE), a urethane
acrylate, an aliphatic urethane acrylate (e.g., aliphatic
difunctional acrylate, aliphatic trifunctional acrylate, aliphatic
multifunctional acrylate), an aromatic urethane acrylate (e.g.,
aromatic difunctional acrylate, aromatic trifunctional acrylate,
aromatic multifunctional acrylate), a polyester acrylate (e.g.,
trifunctional polyester acrylate, tetrafunctional polyester
acrylate, difunctional polyester acrylate, hexafunctional polyester
acrylate), a silicone acrylate (e.g., silicone urethane acrylate,
silicone polyester acrylate), a melamine acrylate, a dendritic
acrylate, an acrylic acrylate, a caprolactone monomer acrylate
(e.g., caprolactone methacrylate, caprolactone acrylate), an oligo
amine acrylate (e.g., amine acrylate, aminated polyester acrylate),
a derivative thereof, or a combination thereof. Non-limiting
examples of aliphatic urethane acrylates include difunctional
aliphatic acrylates (e.g., Miramer PU210, Miramer PU2100, Miramer
PU2560, Miramer SC2404, Miramer SC2565, Miramer UA5216, Miramer
U307, Miramer U3195, or Photocryl DP102), trifunctional aliphatic
acyrlates (e.g., Miramer PU320, Miramer PU340, Miramer PU3450,
Miramer U375, or Photocryl DP225), tetrafunctional aliphatic
acrylates (e.g., Miramer U3304), hexafunctional aliphatic acrylates
(e.g., Miramer MU9800), and multifunctional aliphatic acrylates
(e.g., Miramer MU9800 or Miramer SC2152).
In some embodiments, the toughness modifier comprises acrylic
monomers selected from n-butyl acrylate, iso-decyl acrylate,
n-decyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate,
2-ethylhexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, n-hexyl
acrylate, 2-methoxyethylacrylate, n-octyl methacrylate,
2-phenylethyl acrylate, n-propyl acrylate, and tetrahydrofurfuryl
acrylate. In some embodiments, the toughness modifier is a
poly(ethersulfone), a poly(sulfone), a poly(etherimide), or a
combination thereof. In certain embodiments, the toughness modifier
is a polypropylene or a polypropylene derivative. In some
embodiments, the toughness modifier is a rubber or a rubber
derivative. In certain embodiments, the toughness modifier is a
polyethylene or a derivative thereof. In some embodiments, the
toughness modifier comprises fluorinated acrylic monomers, which
can be selected from 1H,1H-heptafluorobutyl acrylate,
1H,1H,3H-hexafluorobutyl acrylate, 1H,1H,5H-octafluoropentyl
acrylate, or 2,2,2-trifluoroethyl acrylate.
In some embodiments, the toughness modifier is acetaldehyde, allyl
glycidyl ether, trans-butadiene, 1-butene, butyl acrylate,
sec-butyl acrylate, benzyl acrylate, butyl glydicyl ether, butyl
methacrylate, butyl vinyl ether, .epsilon.-caprolactone,
cis-chlorobutadiene, trans-chlorobutadiene, 2-cyanoethyl acrylate,
cyclohexyl acrylate, diethylaminoethyl methacrylate, isobutyl
acrylate, isobutylene, isobutyl vinyl ether, cis-isoprene,
trans-isoprene, isotatic isopropyl acrylate, 2-methoxyethyl
acrylate, methyl acrylate, methyl glicidyl ether,
methylphenylsiloxane, methyl vinyl ether, octadecyl methacrylate,
1-octene, octyl methacrylate, dimethylsiloxane, dodecyl acrylate,
dodecyl methacrylate, dodecyl vinyl ether, epibromohydrin,
epichlorohydrin, 1,2-epoxybutane, 1,2-epoxydecane, 1,2-epoxyoctane,
2-ethoxyethyl acrylate, ethyl acrylate, HDPE ethylene, ethylene
adipate, ethylene-trans-1,4-cyclohexyldicarboxylate, ethylene
malonate, ethylene oxide, 2-ethylhexyl acrylate, 2-ethylhexyl
methacrylate, 2-ethylhexyl vinyl ether, ethyl vinyl ether,
formaldehyde, hexyl acrylate, hexadecyl methacrylate, hexyl
methacrylate, atactic propylene, isotactic propylene, sydiotatic
propylene, propylene oxide, propyl vinyl ether, tetrahydrofuran,
tetramethylene adipate, 2,2,2-trifluoroethyl acrylate, trimethylene
oxide, vinylidene chloride, vinylidene fluoride, vinyl propionate,
a derivative thereof, or a combination thereof.
In some embodiments, the toughness modifier (also referred to
herein as the toughening modifier) comprises a chlorinated
polyethylene, a methacrylate, a copolymer of a chlorinated
polyethylene and methacrylate, a derivative thereof, or a
combination thereof. In some embodiments, the toughening modifier
is a rubber powder. In some embodiments, the toughening modifier is
an anhydride-grafted polymer, an anhydride polymer, or a
combination thereof containing epoxy groups. In certain
embodiments, the anhydride-grafted polymer is a grafted
anhydride-modified thermoplastic elastomer, and can comprise a
styrene-based thermoplastic elastomer comprising styrene units and
units of an olefin (e.g. ethylene, propylene or butene), such as a
styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS),
styrene-ethylene-butadiene-styrene (SEBS),
styrene-ethylene-propylene-styrene (SEPS) copolymers. Suitable
anhydrides include unsaturated carboxylic acid anhydride, wherein
the carboxylic acid is an acrylic acid, methacrylic acid,
.alpha.-methyl acrylic acid, maleic acid, fumaric acid, itaconic
acid, citraconic acid, tetrahydrophthalic acid,
methyl-tetrahydrophthalic acid, or combinations thereof.
Specific toughness modifiers suitable for use in the subject
compositions are described herein below, including compounds of
formula (II), (III), (IV) or (V). In some embodiments, the
toughness modifier is selected from UA5216 (Miwon), a compound of
formula (II), a compound of formula (III), a compound of formula
(IV), a compound of formula (V), TNM1, TNM2, TNM3, TNM4, TNM5, and
TNM6.
A reactive diluent of the subject compositions typically has a low
viscosity. One or more reactive diluents may be included in the
composition to reduce the viscosity of the composition, e.g., to a
viscosity less than the viscosity of the composition in the absence
of the reactive diluent. The reactive diluent(s) may reduce the
viscosity of the composition by at least 10%, such as by at least
20%, at least 30%, at least 40%, at least 50%, at least 60%, at
least 70%, at least 80%, or at least 90%. The curable composition
can comprise 5 to 80 wt %, 5 to 70 wt %, 5 to 60 wt %, 5 to 50 wt
%, 5 to 40 wt %, 5 to 30 wt %, 5 to 25 wt %, 5 to 20 wt %, 10 to 70
wt %, 10 to 60 wt %, 10 to 50 wt %, 10 to 40 wt %, 10 to 30 wt %,
10 to 25 wt %, 20 to 70 wt %, 20 to 60 wt %, 20 to 50 wt %, 20 to
40 wt %, 20 to 35 wt %, or 20 to 30 wt %, based on the total weight
of the composition, of the reactive diluent. In certain
embodiments, the curable composition may comprise 5 to 80 wt %,
based on the total weight of the composition, of the reactive
diluent. In certain embodiments, the curable composition may
comprise 5 to 50 wt %, based on the total weight of the
composition, of the reactive diluent. The reactive diluent of the
curable composition may be monofunctional. In some embodiments, the
reactive diluent comprises a methacrylate. In some embodiments, the
reactive diluent comprises a dimethacrylate. The reactive diluent
may be selected from the group consisting of dimethacrylates of
polyglycols, hydroxybenzoic acid ester (meth)acrylates, and
mixtures thereof. Optionally, the reactive diluent is a cycloalkyl
2-, 3- or 4-((meth)acryloxy)benzoate. In some embodiments, the
reactive diluent is a compound of formula (VII):
##STR00006## wherein:
R.sub.8 represents optionally substituted C.sub.3-C.sub.10
cycloalkyl, optionally substituted 3- to 10-membered
heterocycloalkyl, or optionally substituted C.sub.6-C.sub.10
aryl;
R.sub.9 represents H or C.sub.1-C.sub.6 alkyl;
each R.sub.10 independently represents halo, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 alkoxy, Si(R.sub.u).sub.3, P(O)(OR.sub.12).sub.2,
or N(R.sub.13).sub.2; each R.sub.11 independently represents
C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 alkoxy;
each R.sub.12 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.6-C.sub.10 aryl;
each R.sub.13 independently represents H or C.sub.1-C.sub.6
alkyl;
X is absent, C.sub.1-C.sub.3 alkylene, 1- to 3-membered
heteroalkylene, or (CH.sub.2CH.sub.2O).sub.r;
Y is absent or C.sub.1-C.sub.6 alkylene;
q is an integer from 0 to 4; and
r is an integer from 1 to 4.
In some embodiments, for a compound of formula (VII), R.sub.8 may
be unsubstituted or substituted with one or more substituents
selected from the group consisting of C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.7 cycloalkyl,
C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6-alkoxy-C.sub.6-C.sub.10-aryl,
--O(CO)--(C.sub.1-C.sub.6)alkyl, --COO--(C.sub.1-C.sub.6)alkyl,
.dbd.O, --F, --Cl, and --Br. Specific reactive diluents suitable
for use in the subject compositions are described herein below,
including compounds of formula (VI) and (VII). In some embodiments,
the reactive diluent is selected from TEGDMA (triethylene glycol
dimethacrylate) (Aldrich), D4MA (1,12-dodecanediol dimethacrylate)
(Aldrich), HSMA (3,3,5-trimethylcyclohexyl
2-(methacryloxy)benzoate) (EAG), BSMA (benzyl salicylate
methacrylate) (EAG), a compound of formula (VI), and a compound of
formula (VII).
A curable composition of the present disclosure may further
comprise 0 to 50 wt %, based on the total weight of the
composition, of a glass transition temperature (T.sub.g) modifier
(also referred to herein as a T.sub.g modifier, a glass transition
modifier, a crosslinker, and a cross-linker). The T.sub.g modifier
can have a high glass transition temperature, which leads to a high
heat deflection temperature, which can be necessary to use a
material at elevated temperatures. In some embodiments, the curable
composition comprises 0 to 80 wt %, 0 to 75 wt %, 0 to 70 wt %, 0
to 65 wt %, 0 to 60 wt %, 0 to 55 wt %, 0 to 50 wt %, 1 to 50 wt %,
2 to 50 wt %, 3 to 50 wt %, 4 to 50 wt %, 5 to 50 wt %, 10 to 50 wt
%, 15 to 50 wt %, 20 to 50 wt %, 25 to 50 wt %, 30 to 50 wt %, 35
to 50 wt %, 0 to 40 wt %, 1 to 40 wt %, 2 to 40 wt %, 3 to 40 wt %,
4 to 40 wt %, 5 to 40 wt %, 10 to 40 wt %, 15 to 40 wt %, or 20 to
40 wt % of a T.sub.g modifier. In certain embodiments, the curable
composition comprises 0-50 wt % of a glass transition modifier. The
T.sub.g modifier typically has a higher T.sub.g than the toughness
modifier. Optionally, the number average molecular weight of the
T.sub.g modifier is 0.4 to 5 kDa. In some embodiments, the number
average molecular weight of the T.sub.g modifier is from 0.1 to 5
kDa, from 0.2 to 5 kDa, from 0.3 to 5 kDa, from 0.4 to 5 kDa, from
0.5 to 5 kDa, from 0.6 to 5 kDa, from 0.7 to 5 kDa, from 0.8 to 5
kDa, from 0.9 to 5 kDa, from 1.0 to 5 kDa, from 0.1 to 4 kDa, from
0.2 to 4 kDa, from 0.3 to 4 kDa, from 0.4 to 4 kDa, from 0.5 to 4
kDa, from 0.6 to 4 kDa, from 0.7 to 4 kDa, from 0.8 to 4 kDa, from
0.9 to 4 kDa, from 1 to 4 kDa, from 0.1 to 3 kDa, from 0.2 to 3
kDa, from 0.3 to 3 kDa, from 0.4 to 3 kDa, from 0.5 to 3 kDa, from
0.6 to 3 kDa, from 0.7 to 3 kDa, from 0.8 to 3 kDa, from 0.9 to 3
kDa, or from 1 to 3 kDa. The toughness modifier, the reactive
diluent and the T.sub.g modifier are typically miscible and
compatible in the methods described herein. When used in the
subject compositions, the T.sub.g modifier may provide for high
T.sub.g and strength values, sometimes at the expense of elongation
at break. The toughness modifier may provide for high elongation at
break and toughness via strengthening effects, and the reactive
diluent may improve the processability of the formulations,
particularly of those comprising high amounts of toughness
modifiers, while maintaining high values for strength and
T.sub.g.
The T.sub.g modifier may comprise a urethane group. In some
embodiments, the T.sub.g modifier comprises at least one
methacrylate group. The curable composition may comprise 10 to 20
wt %, based on the total weight of the composition, of the T.sub.g
modifier. The T.sub.g modifier may comprise a urethane group. In
some embodiments, the T.sub.g modifier comprises at least one
methacrylate group. The curable composition may comprise 20 to 40
wt %, based on the total weight of the composition, of the T.sub.g
modifier. The T.sub.g modifier may comprise a urethane group. In
some embodiments, the T.sub.g modifier comprises at least one
methacrylate group. The curable composition may comprise 10 to 50
wt %, based on the total weight of the composition, of the T.sub.g
modifier. Specific T.sub.g modifiers suitable for use in the
subject compositions are described herein below, including
compounds of formula (I). In some embodiments, the T.sub.g modifier
is selected from H1188
(bis((2-((methacryloyloxy)methypoctahydro-1H-4,7-methanoinden-5-yl)methyl-
)cyclohexane-1,4-dicarboxylate), TGM1, TGM2, TGM3, TGM4, and a
compound of formula (I). In some embodiments, the T.sub.g modifier
is a derivative of H1188 (DMI), TGM1, TGM2, TGM3, TGM4, or a
derivative of the compound of formula (I). In some embodiments, the
T.sub.g modifier is a blend of modifiers comprising H1188 (DMI),
TGM1, TGM2, TGM3, TGM4, or a compound of formula (I). In some
embodiments, the T.sub.g modifier is H1188:
##STR00007## In some embodiments, the T.sub.g modifier is TGM1:
##STR00008## In some embodiments, the T.sub.g modifier is TGM2:
##STR00009## In some embodiments, the T.sub.g modifier is TGM3:
##STR00010## In some embodiments, the T.sub.g modifier is TGM4:
##STR00011## In some embodiments, the T.sub.g modifier is a
compound of Formula (I):
##STR00012## wherein:
each R.sub.1 and each R.sub.2 independently represent a divalent,
linear, branched or cyclic C.sub.5-C.sub.15 aliphatic radical, with
the proviso that at least one of R.sub.1 and R.sub.2 is or
comprises a C.sub.5-C.sub.6 cycloaliphatic structure,
each R.sub.3 independently represents a divalent, linear or
branched C.sub.2-C.sub.4 alkyl radical, and n is an integer from 1
to 5,
with the proviso that R.sub.1, R.sub.2, R.sub.3 and n are selected
so as to result in a number average molecular weight of the
oligomeric dimethacrylate from 0.4 to 5 kDa.
In some embodiments, the T.sub.g modifier comprises a plurality of
aliphatic rings. In certain embodiments, the T.sub.g modifier
comprises a plurality of aliphatic rings. In some embodiments, the
aliphatic rings are hydrocarbon rings. In some embodiments, the
aliphatic rings are saturated. In some embodiments, the plurality
of aliphatic rings comprise cyclobutane, cyclopentane, cyclohexane,
cycloheptane, cyclooctane, cyclononane, cyclodecane, or any
combination thereof. In some embodiments, the plurality of
aliphatic rings include bridged ring structures. In some
embodiments, the plurality of aliphatic rings include fused ring
structures. In certain embodiments, the middle portion of the
T.sub.g modifier comprises a cyclohexane-1,4-dicarboxylic acid, a
cyclohexanedimethanol, a
cyclohexane-1,4-diylbis(methylene)dicarbamate, or a combination
thereof. In certain embodiments, the center of the T.sub.g modifier
structure comprises a cyclohexane-1,4-diylbis(methylene)dicarbamate
(e.g., TGM1, TGM2, and TGM3).
In some embodiments, the T.sub.g modifier comprises a methacrylate.
In some embodiments, the T.sub.g modifier comprises at least two
methacrylates. In certain embodiments, the T.sub.g modifier has
terminal portions comprising methacrylates. In some embodiments,
the T.sub.g modifier has a structure that terminates at each end
with a methacrylate. In some embodiments, the T.sub.g modifier is a
bis(2-methacrylate) (e.g., TGM1, TGM2, TGM3, TGM4, and H1188).
In some embodiments, the T.sub.g modifier comprises a blend of
components, selected from TGM1, TGM2, TGM3, TGM4, H1188, a compound
of formula (I), D3MA (1,10-decanediol dimethacrylate), D4MA
(1,12-dodecanediol dimethacrylate), RDI, LPU624, a derivative
thereof, or a combination thereof.
A curable composition of the present disclosure may further
comprise 0.1 to 10 wt %, based on the total weight of the
composition, of an additive. Additives may increase the performance
or processibility of the composition in direct or additive
manufacturing processes. The additive may be selected from a resin,
a defoamer and a surfactant, or a combination thereof. A resin
included in the composition as an additive may be highly
functional, which may reduce the time to gel. One or more defoamers
may be added to the composition to reduce foam in the formulation,
which may lead to fewer defects (e.g., air pockets) in a polymer
prepared from the composition. A surfactant may be added to reduce
surface tension of the composition, which may improve processing in
an additive manufacturing process, such as 3D-printing. In some
embodiments, the composition comprises from 0.01 to 20 wt %, from
0.01 to 15 wt %, from 0.01 to 10 wt %, from 0.01 to 9 wt %, from
0.01 to 8 wt %, from 0.01 to 7 wt %, from 0.01 to 6 wt %, from 0.01
to 5 wt %, from 0.1 to 10 wt %, from 0.1 to 9 wt %, from 0.1 to 8
wt %, from 0.1 to 7 wt %, from 0.1 to 6 wt %, from 0.1 to 5 wt %,
from 0.5 to 10 wt %, from 0.5 to 9 wt %, from 0.5 to 8 wt %, from
0.5 to 7 wt %, from 0.5 to 6 wt %, from 0.5 to 5 wt %, from 1 to 10
wt %, from 1 to 9 wt %, from 1 to 8 wt %, from 1 to 7 wt %, from 1
to 6 wt %, or from 1 to 5 wt %, based on the total weight of the
composition, of an additive. In some embodiments, the composition
comprises 0.3 to 3.5 wt %, based on the total weight of the
composition, of an additive. In some embodiments, the defoamer
comprises a modified urea (e.g., BYK.RTM.-7411 ES, BYK.RTM.-7420
ES, and BYK.RTM.-7410 ET), a silicone-free foam-destroying polymer
(e.g., BYK.RTM.-A 535), a composition having a short siloxane
backbone and long organic modifications (e.g., TEGO.RTM. RAD 2100),
a silica-base defoamer, a hydrophobic silica, a wax, a fatty
alcohol, a fatty acid, or a wetting component (e.g., a
silicone-free wetting compound, such as TEGO.RTM. Wet 510). In some
embodiments, the defoamer is selected from the group consisting of
BYK.RTM.-7411 ES, BYK.RTM.-7420 ES, BYK.RTM.-7410 ET, BYK.RTM.-A
535, TEGO.RTM. RAD2100, and TEGO.RTM. WET510. In some embodiments,
the additive is a surfactant selected from the group consisting of
an amphoteric surfactant, a zwitterionic surfactant, an anionic
surfactant, a nonionic surfactant, a cationic surfactant, or any
combination thereof. The cationic surfactant is selected from
quaternary salts, certain amines and combinations thereof. In some
embodiments, the additive is selected from SIU2400 (Miwon), BDT1006
(Dymax), BYK.RTM.-430, and BYK.RTM.-A535.
In some embodiments, the composition further comprises 0.05 to 1 wt
%, 0.05 to 2 wt %, 0.05 to 3 wt %, 0.05 to 4 wt %, 0.05 to 5 wt %,
0.1 to 1 wt %, 0.1 to 2 wt %, 0.1 to 3 wt %, 0.1 to 4 wt %, 0.1 to
5 wt %, 0.1 to 6 wt %, 0.1 to 7 wt %, 0.1 to 8 wt %, 0.1 to 9 wt %,
or 0.1 to 10 wt %, based on the total weight of the composition, of
a photoblocker. The photoblocker can absorb irradiation and prevent
or decrease the rate of polymerization or degradation, and its
addition to the curable composition can increase the resolution of
printable materials. In certain embodiments, the photoblocker
comprises a hydroquinone, 1,4-dihydroxybenzene, a compound
belonging to the HALS (hindered-amine light stabilizer) family, a
benzophenone, a benzotriazole, any derivative thereof, or any
combination thereof. In some embodiments, the photoblocker
comprises 2,2'-dihydroxy-4-methoxybenzophenone. In certain
embodiments, the photoblocker is selected from the group consisting
of Michler's ketone, 4-Allyloxy-2-hydroxybenzophenone 99%,
2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
powder, 2-(2H-Benzotriazol-2-yl)-4,6-di-tert-pentylphenol,
2-(2H-Benzotriazol-2-yl)-6-dodecyl-4-methylphenol,
2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate,
2-(2H-Benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol,
2-(2H-Benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol,
2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate,
3,9-Bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]unde-
cane, Bis(octadecyl)hydroxylamine powder,
3,9-Bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane,
Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,
Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
2-tert-Butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol,
2-tert-Butyl-4-ethylphenol, 5-Chloro-2-hydroxybenzophenone,
5-Chloro-2-hydroxy-4-methylbenzophenone,
2,4-Di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol,
2,6-Di-tert-butyl-4-(dimethylaminomethyl)phenol,
3',5'-Dichloro-2'-hydroxyacetophenone, Didodecyl
3,3'-thiodipropionate, 2,4-Dihydroxybenzophenone,
2,2'-Dihydroxy-4-methoxybenzophenone,
2',4'-Dihydroxy-3'-propylacetophenone, 2,3-Dimethylhydroquinone,
2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol,
5-Ethyl-1-aza-3,7-dioxabicyclo[3.3.0]octane, Ethyl
2-cyano-3,3-diphenylacrylate, 2-Ethylhexyl
2-cyano-3,3-diphenylacrylate, 2-Ethylhexyl
trans-4-methoxycinnamate, 2-Ethylhexyl salicylate,
2-Hydroxy-4-(octyloxy)benzophenone, Menthyl anthranilate,
2-Methoxyhydroquinone, Methyl-p-benzoquinone,
2,2'-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)ph-
enol], 2,2'-Methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-Methylenebis(6-tert-butyl-4-methylphenol),
5,5'-Methylenebis(2-hydroxy-4-methoxybenzophenone),
Methylhydroquinone, 4-Nitrophenol sodium salt hydrate, Octadecyl
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Pentaerythritol
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
2-Phenyl-5-benzimidazolesulfonic acid,
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6--
tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piper-
idyl)imino], Sodium D-isoascorbate monohydrate,
Tetrachloro-1,4-benzoquinone, Triisodecyl phosphite,
1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
Tris(2,4-di-tert-butylphenyl)phosphite,
1,3,5-Tris(2-hydroxyethyl)isocyanurate, and
Tris(nonylphenyl)phosphite
In some embodiments, the photoblocker has a maximum wavelength
absorbance between 200 and 300 nm, between 300 and 400 nm, between
400 and 500 nm, between 500 and 600 nm, between 600 and 700 nm,
between 700 and 800 nm, between 800 and 900 nm, between 150 and 200
nm, between 200 and 250 nm, between 250 and 300 nm, between 300 and
350 nm, between 350 and 400 nm, between 400 and 450 nm, between 450
and 500 nm, between 500 and 550 nm, between 550 and 600 nm, between
600 and 650 nm, between 650 and 700 nm, or between 700 and 750 nm.
In some embodiments, the photoblocker has a maximum wavelength
absorbance between 300 to 500 nm, such as 300 to 400 nm or 350 to
480 nm.
In some embodiments, the composition further comprises 0.05 to 1 wt
%, 0.05 to 2 wt %, 0.05 to 3 wt %, 0.05 to 4 wt %, 0.05 to 5 wt %,
0.1 to 1 wt %, 0.1 to 2 wt %, 0.1 to 3 wt %, 0.1 to 4 wt %, 0.1 to
5 wt %, 0.1 to 6 wt %, 0.1 to 7 wt %, 0.1 to 8 wt %, 0.1 to 9 wt %,
or 0.1 to 10 wt %, based on the total weight of the composition, of
a photoinitiator. In some embodiments, the photoinitiator is a free
radical photoinitiator. In certain embodiments, the free radical
photoinitiator comprises an alpha hydroxy ketone moiety (e.g.,
2-hydroxy-2-methylpropiophenone or 1-hydroxycyclohexyl phenyl
ketone), an alpha-amino ketone (e.g.,
2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone or
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one),
4-methyl benzophenone, an azo compound (e.g.,
4,4'-Azobis(4-cyanovaleric acid),
1,1'-Azobis(cyclohexanecarbonitrile, Azobisisobutyronitrile,
2,2'-Azobis(2-methylpropionitrile), or
2,2'-Azobis(2-methylpropionitrile)), an inorganic peroxide, an
organic peroxide, or any combination thereof. In some embodiments,
the composition comprises a photoinitiator comprising SpeedCure
TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate). In some
embodiments, the composition comprises a photoinitiator selected
from a benzophenone, a mixture of benzophenone and a tertiary amine
containing a carbonyl group which is directly bonded to at least
one aromatic ring, and an Irgacure (e.g., Irgacure 907
(2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1) or
Irgacure 651 (2,2-dimethoxy-1,2-diphenylethan-1-one). In some
embodiments, the photoinitiator comprises an acetophenone
photoinitiator (e.g., 4'-hydroxyacetophenone,
4'0phenoxyacetophenone, 4'-ethoxyacetophenone), a benzoin, a
benzoin derivative, a benzil, a benzil derivative, a benzophenone
(e.g., 4-benzoylbiphenyl, 3,4-(dimethylamino)benzophenone,
2-methylbenzophenone), a cationic photoinitiator (e.g.,
diphenyliodonium nitrate, (4-iodophenyl)diphenylsulfonium triflate,
triphenylsulfonium triflate), an anthraquinone, a quinone (e.g.,
camphorquinone), a phosphine oxide, a phosphinate,
9,10-phenanthrenequinone, a thioxanthone, any combination thereof,
or any derivative thereof.
In some embodiments, the photoinitiator has a maximum wavelength
absorbance between 200 and 300 nm, between 300 and 400 nm, between
400 and 500 nm, between 500 and 600 nm, between 600 and 700 nm,
between 700 and 800 nm, between 800 and 900 nm, between 150 and 200
nm, between 200 and 250 nm, between 250 and 300 nm, between 300 and
350 nm, between 350 and 400 nm, between 400 and 450 nm, between 450
and 500 nm, between 500 and 550 nm, between 550 and 600 nm, between
600 and 650 nm, between 650 and 700 nm, or between 700 and 750 nm.
In some embodiments, the photoinitiator has a maximum wavelength
absorbance between 300 to 500 nm.
In some embodiments, the additive is a branched dendritic oligomer.
In some embodiments, the additive has one or more, two or more,
three or more, four or more, five or more, six or more, seven or
more, eight or more, nine or more, ten or more, or greater than 10
functional groups. In some embodiments, the additive has one or
more, two or more, three or more, four or more, five or more, six
or more, seven or more, eight or more, nine or more, ten or more,
or greater than 10 acrylate functional groups. In certain
embodiments, the branched dendritic oligomer additive is a
dendritic acrylate oligomer. In some embodiments, the dendritic
acrylate oligomer is Bomar.TM. BDT-1006, Bomar.TM. BDT-1018,
Bomar.TM. BDT-4330, and the like. In some embodiments, the
multi-functional additive comprises a silicone urethane acrylate.
As a non-limiting example, the silicone urethane acrylate can have
1 functional group, 2 functional groups, 3 functional groups, 4
functional groups, 5 functional groups, 6 functional groups, 7
functional groups, 8 functional groups, 9 functional groups, 10
functional groups, 11 functional groups, 12 functional groups, 13
functional groups, 14 functional groups, 15 functional groups, 16
functional groups, 17 functional groups, 18 functional groups, 19
functional groups, 20 functional groups, or greater than 20
functional groups. In some embodiments, the additive can be a
silicone urethane acrylate or comprises a silicone urethane
acrylate. As a non-limiting example, the silicone urethane acrylate
can have 1 acrylate group, 2 acrylate groups, 3 acrylate groups, 4
acrylate groups, 5 acrylate groups, 6 acrylate groups, 7 acrylate
groups, 8 acrylate groups, 9 acrylate groups, 10 acrylate groups,
11 acrylate groups, 12 acrylate groups, 13 acrylate groups, 14
acrylate groups, 15 acrylate groups, 16 acrylate groups, 17
acrylate groups, 18 acrylate groups, 19 acrylate groups, 20
acrylate groups, or greater than 20 acrylate groups. As
non-limiting examples of silicone acrylates, the additive can be
Miramer SIU2400 (a silicone urethane acrylate having a
functionality number of 10, diluted with 10% TPGDA) or SIP910 (a
silicone polyester acrylate having a functionality number of
2).
In certain aspects, the present disclosure provides a curable
composition for use in a high temperature lithography-based
photopolymerization process, said composition comprising the
following polymerizable Components A to C,
Component A being at least one oligomeric dimethacrylate according
to the following chemical formula (I), serving as a glass
transition temperature modifier:
##STR00013## wherein:
each R.sub.1 and each R.sub.2 independently represent a divalent,
linear, branched or cyclic C.sub.5-C.sub.15 aliphatic radical, with
the proviso that at least one of R.sub.1 and R.sub.2 is or
comprises a C.sub.5-C.sub.6 cycloaliphatic structure,
each R.sub.3 independently represents a divalent, linear or
branched C.sub.2-C.sub.4 alkyl radical, and
n is an integer from 1 to 5,
with the proviso that R.sub.1, R.sub.2, R.sub.3 and n are selected
so as to result in a number average molecular weight of the
oligomeric dimethacrylate from 0.4 to 5 kDa;
Component B being at least one, optionally polyether-modified,
(poly)carbonate-(poly)urethane dimethacrylate according to any one
of the following chemical formulas (II), (III), (IV) or (V),
serving as a toughness modifier:
##STR00014## wherein:
each R.sub.4 and each R.sub.5 independently represent a divalent,
linear, branched or cyclic C.sub.5-C.sub.15 aliphatic radical,
each R.sub.6 independently represents a divalent, linear or
branched C.sub.2-C.sub.4 alkyl radical,
each R.sub.7 independently represents a divalent, linear or
branched C.sub.2-C.sub.6 alkyl radical,
each n is independently an integer from 1 to 10,
each m is independently an integer from 1 to 20,
each o is independently an integer from 5 to 50, and
p is an integer from 1 to 40,
with the proviso that R.sub.4, R.sub.5, R.sub.6, R.sub.7, n, m, o
and p are selected so as to result in a number average molecular
weight of the (poly)carbonate-(poly)urethane dimethacrylate greater
than 5 kDa; and
Component C being at least one mono- or multifunctional
methacrylate-based reactive diluent.
These oligomeric (poly)carbonate-(poly)urethane dimethacrylates
having relatively low molecular weights from 0.4 to 5 kDa, which
are used as glass transition temperature modifiers, and polymeric
(poly)carbonate-(poly)urethane dimethacrylates having high
molecular weights of more than 5 kDa, which are used as tough-ness
modifiers, as defined above, are typically miscible and compatible
due to their related (poly)carbonate-(poly)urethane basic
structures.
When mixed with one or more reactive diluent(s), they result in
curable compositions being well processible at the processing
temperatures usually employed in high temperature lithography-based
photopolymerization processes, i.e. temperatures between 90.degree.
C. and 120.degree. C., as their viscosities at these temperatures
are sufficiently low, despite the presence of the high molecular
weight Component B. Moreover, as such curable compositions comprise
multiple divalent polymerizable components, they result in
crosslinked polymers, more specifically in crosslinked polymers
having excellent thermomechanical properties, as detailed
below.
Preferred compositional ranges of the amounts of these three
components are from 20 to 50 wt % of Component A, from 25 to 50 wt
% of Component B, and from 10 to 40 wt % of Component C, based on
the total weight of the curable composition.
In preferable embodiments of the present disclosure, the "carbonate
radical" R.sub.1 of the glass transition temperature modifiers of
Component A is a divalent radical originating from a diol selected
from the group consisting of 1,4-cyclo-hexanedimethanol (CHDM),
4,4'-isopropylidenedicyclohexanol (HBPA),
4,8-bis-(hydroxymethyl)tricyclo[5.2.1.0.sup.2'.sup.6]decane (HTCD),
3,9-bis(1,1-dimethyl-2-hydroxy-ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane-
, 1,3-bis(hydroxymethyl)adamantane, 1,4-, 1,3- or
1,2-dihydroxycyclohexane, 1,3-adamantanediol,
4-hydroxy-.alpha.,.alpha.,4-trimethyl-cyclohexanemethanol,
2,3-pinanediol, 1,6-hexanediol, and mixtures thereof, more
preferably a divalent radical originating from
1,4-cyclohexanedimethanol (CHDM), as such cyclic structures provide
for a relatively high degree of rigidity of the molecules of
oligomeric dimethacrylate A. Such rigidity may contribute to a
relatively high glass transition temperature of the polymerizates,
i.e. preferably a glass transition temperature>90.degree. C.,
more preferably >100.degree. C.
The "urethane radical" R.sub.2 of the glass transition temperature
modifiers of Component A preferably is a divalent radical
originating from a diisocyanate independently selected from the
group consisting of isophorone diisocyanate (IPDI), hexamethylene
diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI),
dicyclohexylmethane 4,4'-diisocyanate (HMDI),
1,3-bis(isocyanatomethyl)cyclohexane, and mixtures thereof, more
preferably from isophorone diisocyanate (IPDI) or hexamethylene
diisocyanate (HDI). Such cycloaliphatic or short-chained linear
aliphatic structures typically provide for a suitable degree of
rigidity of the glass transition temperature modifiers of Component
A.
In order to provide for high toughness and other mechanical
properties of the polymerizates and also for keeping their glass
transition temperatures relatively high, the "carbonate radical"
R.sub.4 of the toughness modifiers of Component B is preferably a
divalent radical originating from a diol selected from the group
consisting of 2,2-dimethyl-1,3-propanediol (DMP), 1,6-hexanediol,
1,4-cyclohexanedimethanol (CHDM), and mixtures thereof, which more
preferably represents the alcoholic moiety of a polycarbonate-diol.
For the "urethane radical" R.sub.5 the same preferences are valid
as for R.sub.2, which means that R.sub.5 preferably is a divalent
radical originating from a diisocyanate independently selected from
the group consisting of isophorone diisocyanate (IPDI),
hexamethylene diisocyanate (HDI), trimethylhexamethylene
diisocyanate (TMDI), dicyclohexylmethane 4,4'-diisocyanate (HMDI),
1,3-bis(isocyanatomethyl)cyclohexane, and mixtures thereof, more
preferably from isophorone diisocyanate (IPDI) or hexamethylene
diisocyanate (HDI).
In further preferred embodiments, the terminal "methacrylate
radicals" R.sub.3 and R.sub.6 of the modifiers of Components A and
B, respectively, are divalent radicals originating from a
short-chained diol independently selected from the group consisting
of 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol,
1,4-butanediol, and mixtures thereof, more preferably from
1,2-ethanediol, the corresponding methacrylate being hydroxyethyl
methacrylate, HEMA, a frequently used and economic methacrylate
monomers.
As already mentioned above, the optional polyether-modification of
the toughness modifiers of Component B serves as a "soft block" for
providing a softening or plastifying effect for the polymerizates
obtained from the curable composition of the present disclosure,
and it may be positioned between two blocks of a
(poly)carbonate-(poly)urethane shown in formula (II) (between the
two terminal R.sub.6-methacrylate moieties), as depicted in formula
(III), or two polyether blocks may be positioned at both sides of
one block of such (poly)carbonate-(poly)urethane, as depicted in
formula (IV), or polyether blocks and
(poly)carbonate-(poly)urethane blocks may be alternating to give
the polymer depicted in formula (V), each of these combinations of
polyether blocks and (poly)carbonate-(poly)urethane blocks being
terminated by two polymerizable R.sub.6-methacrylate moieties. In
preferred embodiments, the corresponding "ether radical" R.sub.7 of
the polyether-modification is a divalent radical originating from
1,4-butanediol, which means that the polyether used as the
modification preferably is polytetrahydrofuran, which is
commercially available and thus an economic choice.
Generally, any commercially available compounds may be used as the
Components A, B and C of the curable compositions according to the
present disclosure, provided that such compounds meet the
requirements defined herein. Alternatively, the Components A, B and
C may be synthesized by any preparation methods known in the art of
organic synthesis; for example, as exemplified in the synthesis
examples herein.
As mentioned above, Components A and B, more specifically the glass
transition temperature modifiers of Component A and the unmodified
toughness modifiers of Component B represented by formula (II), are
preferably prepared in substantially analogous manners by reacting
a diol comprising the "carbonate radical" R.sub.1 or R.sub.4,
respectively, with a molar excess of diisocyanate comprising the
corresponding "urethane radical" R.sub.2 or R.sub.5, respectively.
For preparing the oligomeric Component A, the molar excess of
diisocyanate is preferably relatively high, for example, in the
range of 1.8 to 2 equivalents, preferably in the range of 1.9 to 2
equivalents, of diisoyanate per 1 equivalent of diol, in order to
yield the desired relatively low molecular weight. On the other
hand, for preparing the relatively high molecular weight polymeric
toughness modifiers of Component B, a smaller molar excess of
diisocyanate may be used, for example, in the range of 1.1 to 1.6
equivalents, preferably in the range of 1.1 to 1.4 equivalents, of
diisoyanate per 1 equivalent of diol, in order to produce the
respective isocyanate-terminated (poly)carbonate-(poly)urethane
molecules. One equivalent each of the oligomer molecule comprising
R.sub.1 and R.sub.2 or the polymeric molecule comprising R.sub.4
and R.sub.5 is finally reacted with (at least) 2 equivalents of an
.omega.-hydroxyalkyl methacrylate comprising the corresponding
"meth-acrylate radical" R.sub.3 or R.sub.6, respectively, to yield
the final oligomeric or polymeric dimethacrylates of Component A or
B, respectively. These synthetic ways are shown in the reaction
schemes below.
##STR00015##
##STR00016##
For convenience, also the polyether-modified embodiments of the
toughness modifiers of Component B represented by formulas (III) to
(V) are preferably prepared in a quite similar way by means of
(poly)addition reactions between diols and diisocyanates. In
preferred embodiments of these syntheses, however, there is--in
addition to the (poly)carbonate-diol comprising "alcohol radical"
R.sub.4--a second species of diol reactant, i.e. a polyether-diol
comprising the "ether radical" R.sub.7, which is also reacted with
diisocyanate.
Depending on the intended position of the polyether block(s), one
of these two diol species may be first reacted with a molar excess
of diisocyanate to produce an isocyanate-terminated, oligomeric
first intermediate which, in turn, is reacted with the second diol
species. Depending on the molar ratios selected, this polymeric
second intermediate is either diol- or isocyanate-terminated. In
the latter case, the second intermediate is simply reacted with the
appropriate .omega.-hydroxyalkyl methacrylate, for example,
2-hydroxyethyl methacrylate (HEMA), to yield the final
polyether-modified Component B. In the case of diol-terminated
second intermediates, the .omega.-hydroxyalkyl methacrylate is
first reacted with an equimolar amount of the respective
diisocyanate to produce an isocyanate-functional methacrylate
reactant.
The reaction scheme below shows a preferred synthetic way for
preparing a polyether-modified (poly)carbonate-(poly)urethane
dimethacrylate according to formula (III). First, a similar
diisocyanate-terminated intermediate as in Scheme 2 above is
prepared by reacting (poly)carbonate-diol with a molar excess of
diisocyanate, whereafter 2 equivalents of this first intermediate
are reacted with 1 equivalent of polyether-diol to yield an
isocyanate-terminated second intermediate to which, finally, 2
equivalents of .omega.-hydroxyalkyl methacrylate are added, thus
producing a polyether-modified toughness modifier represented by
formula (III).
##STR00017##
Alternatively, however, toughness modifiers according to formula
(III) can also be synthesized by reacting the R.sub.7-containing
polyether block with 2 equivalents of R.sub.5-containing
diisocyanate, thus producing an isocyanate-terminated first
intermediate, which in turn is reacted with 2 equivalents of the
R.sub.4-containing (poly)carbonate-diol, yielding a diol-terminated
second intermediate. Further, the R.sub.6-containing
.omega.-hydroxyalkyl methacrylate is reacted with an equimolar
amount of the R.sub.5-containing diisocyanate to produce an
isocyanate-functional methacrylate reactant, 2 equivalents of which
are then reacted with the diol-terminated second intermediate to
give Component B according to formula (III).
This synthetic way was followed in Synthesis Example 10 for
synthesizing toughness modifier TNM6, comprising the preparation of
first and second intermediates designated TNM6-A and TNM6-B,
respectively, and of an isocyanate-functional methacrylate
reactant, designated IUEM ("isocyanoisophorone-urethane
ethylmethacrylate").
In a similar way, toughness modifiers according to formulas (IV) or
(V) can be synthesized. For preparing those of formula (IV), again,
an isocyanate-terminated first intermediate similar to that of
Scheme 2 or Scheme 3 is synthesized by reacting the
(poly)carbonate-diol with 2 equivalents of diisocyanate, which in
turn is reacted with 2 equivalents of polyether-diol, yielding a
diol-terminated second intermediate which is finally reacted with 2
equivalents of isocyanate-functionalized methacrylate reactant.
This synthetic way is shown in Scheme 4 below.
Since the toughness modifiers of formula (IV) comprise double the
number of polyether modifications than those according to formula
(III), it may be preferable to provide for more rigid
(poly)carbonate-urethane blocks by selecting relatively
short-chained or cyclic radicals R.sub.4 and/or R.sub.5.
Additionally, or alternatively, it may be preferable to select a
short-chained "ether radical" R.sub.7, in order not to affect the
toughness-raising or -stabilizing effect of Component B.
##STR00018##
For synthesizing toughness modifiers according to formula (V),
again, an isocyanate-terminated first intermediate similar to that
of Schemes 2 to 4 is synthesized by reacting the
(poly)carbonate-diol with 2 equivalents of diisocyanate. However,
in the present case, this first intermediate is reacted with an
equimolar amount of polyether-diol, which yields relatively
long-chained polyaddition products comprising alternating
urethane-carbonate blocks and polyether blocks as well as both
isocyanate and hydroxyl terminal groups. This polyaddition reaction
may be quenched by adding either monoisocyanate or monohydroxy
terminating monomers, preferably either an .omega.-hydroxyalkyl
methacrylate or its isocyanate-functionalized derivative, e.g. as
shown in the first line of Scheme 4 above. The molecular weight of
the thus obtained second intermediate may be controlled by
appropriately selecting the reaction time until addition of the
terminating monomer.
This second intermediate is methacrylate-terminated at one end and
still either hydroxy- or isocyanate-terminated at the other. For
introducing the second methacrylate terminal group, the second
intermediate is reacted with the other species of terminating
monomers, i.e. the .omega.-hydroxyalkyl methacrylate or its
isocyanate-functionalized derivative. If the .omega.-hydroxyalkyl
methacrylate was used to quench the polyaddition reaction, the
second intermediate is finally reacted with its
isocyanate-functionalized derivative, or vice versa. In Scheme 5
below, the contrary reaction is shown, i.e. the polyaddition is
quenched by adding the isocyanate-functionalized methacrylate, and
the second intermediate thus obtained is finally reacted with the
.omega.-hydroxyalkyl methacrylate to yield the toughness modifier
of Component B represented by formula (V).
Since the toughness modifiers of formula (V) typically comprise the
highest number of polyether-modifications, i.e. where p is
.gtoreq.3, it may be preferable to select quite short-chained
radicals R.sub.4, R.sub.5 and/or R.sub.7, and/or or cyclic radicals
R.sub.4 or R.sub.5.
##STR00019##
As mentioned above, a skilled artisan will be able to devise
alternative ways of synthesizing glass transition temperature or
toughness modifiers according to formulas (I) to (V).
As already mentioned above, according to the present disclosure,
the reactive diluent of Component C is not particularly limited, so
that any common species of reactive diluents may be used, as long
as it is compatible with the modifiers of Components A and B.
Preferable diluents, however, are the common, cost-efficient
diluent TEGDMA (triethylene glycol dimethacrylate) and particularly
2-, 3- or 4-((meth)-acryloxy)benzoic acid esters, or 2-, 3- or
4-hydroxybenzoic acid ester (meth)acrylates, such as substituted
cycloalkyl 2-, 3- or 4-((meth)acryloxy)benzoates, the latter having
yielded very good results, as will be shown in the experimental
section below. More preferably, the reactive diluent is an
optionally substituted 2-, 3- or 4-((meth)-acryloxy)benzoic acid
ester according to the following formula (VI):
##STR00020## wherein:
R.sub.8 represents a C.sub.5-C.sub.20 cycloaliphatic hydrocarbyl
radical selected from the group consisting of optionally
substituted C.sub.5-C.sub.7 cycloalkyl radicals;
R.sub.9 represents H or CH.sub.3;
each R.sub.10 independently represents C.sub.1-C.sub.3 alkyl or
C.sub.1-C.sub.3 alkoxy; and
q is an integer from 0 to 4.
In more preferred embodiments of the invention, the reactive
diluent is a 2-, 3- or 4-((meth)acryloxy)benzoic acid ester
according to formula (VI), wherein R.sub.8 is selected from the
group consisting of optionally substituted C.sub.5-C.sub.7
cycloalkyl radicals having 5 to 15, more preferably 5 to 12, most
preferably 5 to 10, carbon atoms in total. In even more preferred
embodiments, R.sub.8 is selected from the group consisting of
cyclohexyl radicals substituted with one or more, linear or
branched C.sub.1-C.sub.6 alkyl groups, even more preferably one or
more C.sub.1-C.sub.3 alkyl groups, wherein two of said
C.sub.1-C.sub.6 alkyl groups, or C.sub.1-C.sub.3 alkyl groups, may
be connected to form a ring together with the carbon atoms to which
they are attached and optionally one or more additional,
intervening carbon atoms of the cyclohexyl ring. Such monomers are
typically liquid at room temperature or have suitably low melting
points and show pronounced viscosity-lowering effects. Most
preferably, R.sub.8 is selected from the group consisting of
##STR00021## wherein the broken lines each represent a bond to the
ester oxygen atom.
An exemplary representative of this group, menthyl salicylate
methacrylate, was prepared as disclosed in Synthesis Example 11 and
was used as Reactive Diluent 1 (RD 1) in most of the examples of
the present disclosure.
In some embodiments, the reactive diluent is a compound of formula
(VII):
##STR00022## wherein:
R.sub.8 represents optionally substituted C.sub.3-C.sub.10
cycloalkyl, optionally substituted 3- to 10-membered
heterocycloalkyl, or optionally substituted C.sub.6-C.sub.10
aryl;
R.sub.9 represents H or C.sub.1-C.sub.6 alkyl;
each R.sub.10 independently represents halo, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 alkoxy, Si(R.sub.11).sub.3, P(O)(OR.sub.12).sub.2,
or N(R.sub.13).sub.2;
each R.sub.11 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.1-C.sub.6 alkoxy;
each R.sub.12 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.6-C.sub.10 aryl;
each R.sub.13 independently represents H or C.sub.1-C.sub.6
alkyl;
X is absent, C.sub.1-C.sub.3 alkylene, 1- to 3-membered
heteroalkylene, or (CH.sub.2CH.sub.2O).sub.r;
Y is absent or C.sub.1-C.sub.6 alkylene;
q is an integer from 0 to 4; and
r is an integer from 1 to 4.
In some embodiments, for a compound of formula (VII), R.sub.8 is
selected from optionally substituted C.sub.5-C.sub.10 cycloalkyl
and optionally substituted C.sub.6-C.sub.10 aryl, such as
optionally substituted phenyl. In some embodiments, R.sub.8 is
optionally substituted C.sub.5-C.sub.7 cycloalkyl. The optionally
substituted C.sub.5-C.sub.7 cycloalkyl may have 5 to 15 carbon
atoms in total, such as 5 to 12 or 5 to 10 carbon atoms. For a
compound of formula (VII), R.sub.8 may be a monocyclic cycloalkyl,
such as cyclohexyl. In some embodiments, R.sub.8 is a bicyclic
cycloalkyl, such as a bridged, fused, or spirocyclic cycloalkyl.
This includes, for example, bicyclo[2.2.1]heptyl,
bicyclo[1.1.1]pentyl, spiro[4.4]nonyl, and decahydronaphthyl, each
of which may be optionally substituted. In some embodiments,
R.sub.8 is unsubstituted. In some embodiments, R.sub.8 is
substituted with at least one substituent.
Exemplary optional substituents of R.sub.8 include C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.7 cycloalkyl,
C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6-alkoxy-C.sub.6-C.sub.10-aryl,
--O(CO)--(C.sub.1-C.sub.6)alkyl, --COO--(C.sub.1-C.sub.6)alkyl,
.dbd.O, --F, --Cl, and --Br. In some embodiments, R.sub.8 is
substituted with at least one --CH.sub.3. For example, in some
embodiments R.sub.8 is substituted with one or more --CH.sub.3 and
optionally further substituted with one or more substituents
selected from the group consisting of C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, --O(CO)--(C.sub.1-C.sub.6)alkyl,
--COO--(C.sub.1-C.sub.6)alkyl, .dbd.O, --F, --Cl, and --Br. In some
embodiments, R.sub.8 is substituted with one or more, linear or
branched C.sub.1-C.sub.6 alkyl, such as methyl, ethyl, n-propyl,
iso-propyl, n-butyl, sec-butyl, iso-butyl, or tert-butyl. Two
substituents of R.sub.8, such as two C.sub.1-C.sub.6 alkyl, may be
connected to form a ring. For example, two substituents on a
cyclohexyl group may form a bridge, such as the methylene bridge
found in bicyclo[2.2.1]heptyl. In some embodiments, R.sub.8 is
substituted with one or more substituents selected from the group
consisting of C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 alkoxy.
Exemplary R.sub.8 groups include, but are not limited to
##STR00023## The broken line is used herein to indicate the bond to
the rest of the molecule (e.g., the bond to linker Y of formula
(VII)). Further exemplary --Y--R.sub.8 groups include, but are not
limited to
##STR00024## ##STR00025##
In some embodiments, q is 0 or 1, such as q is 0. In some
embodiments, R.sub.9 is H or CH.sub.3. In some embodiments, X is
C.sub.1-C.sub.3 alkylene, such as methylene. In some embodiments, X
is absent. In some embodiments, Y is C.sub.1-C.sub.3 alkylene.
In certain aspects, the present disclosure provides a method of
producing crosslinked polymers comprising providing a curable
composition described herein; and polymerizing said composition;
thereby producing said crosslinked polymers. The polymerizing may
be carried out using a high temperature lithography-based
photopolymerization process. Optionally, a solid or highly viscous
resin formulation comprising said composition is heated to a
predefined elevated process temperature and is subsequently
irradiated with light of a suitable wavelength to be absorbed by a
photoinitiator, thereby polymerizing and crosslinking the
composition to obtain said crosslinked polymer. The elevated
process temperature may range from 50.degree. C. to 120.degree. C.
In some embodiments, the photopolymerization process is a direct or
additive manufacturing process, such as a 3D printing process.
In certain aspects, the present disclosure provides a crosslinked
polymer for use in an orthodontic appliance, wherein the
crosslinked polymer is characterized by one or more of a stress
relaxation of greater than or equal to 5% of the initial load; and
a glass transition temperature of greater than or equal to
70.degree. C., such as a glass transition temperature of greater
than or equal to 90.degree. C. The crosslinked polymer may further
be characterized by one or more of a tensile modulus greater than
or equal to 100 MPa; a tensile strength at yield greater than or
equal to 5 MPa; an elongation at yield greater than or equal to 4%;
an elongation at break greater than or equal to 5%; a storage
modulus greater than or equal to 300 MPa; and a remaining stress at
2% strain which is greater than or equal to 0.01 MPa after 2 hours
of loading.
In some embodiments, the crosslinked polymer is characterized by a
stress relaxation of 5% to 85% of the initial load, such as 5% to
45%, 15% to 85%, or 20% to 45% of the initial load. In some
embodiments, the crosslinked polymer is characterized by a glass
transition temperature of 90.degree. C. to 150.degree. C. In some
embodiments, the crosslinked polymer is characterized by a tensile
modulus from 100 MPa to 2000 MPa, such as 800 MPa to 2000 MPa. In
some embodiments, the crosslinked polymer is characterized by a
tensile strength at yield of 5 MPa to 85 MPa, such as 20 MPa to 55
MPa. In some embodiments, the crosslinked polymer is characterized
by a tensile strength at yield of 25 MPa to 55 MPa. In some
embodiments, the crosslinked polymer is characterized by an
elongation at yield of 4% to 10%, such as 5% to 10%. In some
embodiments, the crosslinked polymer is characterized by an
elongation at break of 5% to 250%, such as 20% to 250%. In some
embodiments, the crosslinked polymer is characterized by a storage
modulus of 300 MPa to 3000 MPa, such as 750 MPa to 3000 MPa. In
some embodiments, the crosslinked polymer is characterized by a
stress relaxation of 0.01 MPa to 15 MPa, such as 2 MPa to 15 MPa.
In some embodiments, the crosslinked polymer is characterized by a
stress relaxation of greater than or equal to 20% of the initial
load; a glass transition temperature of greater than or equal to
90.degree. C.; a tensile modulus from 800 MPa to 2000 MPa; and an
elongation at break greater than or equal to 20%.
Stress relaxation properties may be assessed using an RSA-G2
instrument from TA Instruments, with a 3-point bending, 2% strain
method. The stress relaxation is typically measured at 37.degree.
C. and 100% relative humidity and reported as the remaining load
after 2 hours, as either the percent (%) of initial load or in
MPa).
The storage modulus is typically measured at 37.degree. C. and is
reported in MPa. The T.sub.g of the crosslinked polymer may be
assessed using dynamic mechanical analysis (DMA) and is provided
herein as the tan .delta. peak. The tensile modulus, tensile
strength, elongation at yield and elongation at break may be
assessed according to ISO 527-2 5B.
A crosslinked polymer described herein may comprise a first
repeating unit having a number average molecular weight of greater
than 5 kDa, wherein the first repeating unit comprises carbonate
and urethane groups. Optionally, the first repeating unit may be
derived from a (poly)carbonate-(poly)urethane dimethacrylate
oligomer. In some embodiments, the number average molecular weight
of the (poly)carbonate-(poly)urethane dimethacrylate oligomer is
between 5 kDa to 20 kDa, such as between 10 kDa to 20 kDa. A
crosslinked polymer described herein may comprise a second
repeating unit having a number average molecular weight of 0.4 to 5
kDa, wherein the second repeating unit comprises a urethane group.
The second repeating unit may be derived from a (poly)urethane
dimethacrylate oligomer. In some embodiments, the crosslinked
polymer comprises a monomer of the formula:
##STR00026## wherein:
R.sub.8 represents optionally substituted C.sub.3-C.sub.10
cycloalkyl, optionally substituted 3- to 10-membered
heterocycloalkyl, or optionally substituted C.sub.6-C.sub.10
aryl;
R.sub.9 represents H or C.sub.1-C.sub.6 alkyl;
each R.sub.10 independently represents halo, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 alkoxy, Si(R.sub.11).sub.3, P(O)(OR.sub.12).sub.2,
or N(R.sub.13).sub.2;
each R.sub.11 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.1-C.sub.6 alkoxy;
each R.sub.12 independently represents C.sub.1-C.sub.6 alkyl or
C.sub.6-C.sub.10 aryl;
each R.sub.13 independently represents H or C.sub.1-C.sub.6
alkyl;
X is absent, C.sub.1-C.sub.3 alkylene, 1- to 3-membered
heteroalkylene, or (CH.sub.2CH.sub.2O).sub.r;
Y is absent or C.sub.1-C.sub.6 alkylene;
q is an integer from 0 to 4; and
r is an integer from 1 to 4
wherein each dashed line represents a bond to a carbon atom.
In some embodiments, R.sub.8 is unsubstituted or substituted with
one or more substituents selected from the group consisting of
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.7
cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6-alkoxy-C.sub.6-C.sub.10-aryl,
--O(CO)--(C.sub.1-C.sub.6)alkyl, --COO--(C.sub.1-C.sub.6)alkyl,
.dbd.O, --F, --Cl, and --Br.
In some embodiments, a crosslinked polymer described herein
comprises 20 to 50 wt % of the first repeating unit based on the
total weight of the crosslinked polymer, such as 25 to 50% of the
first repeating unit based on the total weight of the crosslinked
polymer. A crosslinked polymer described herein may comprise 1 to
50 wt % of the second repeating unit based on the total weight of
the crosslinked polymer, such as 20 to 50 wt % of the second
repeating unit based on the total weight of the crosslinked
polymer. In some embodiments, a crosslinked polymer described
herein comprises 1 to 80 wt % of the monomer based on the total
weight of the crosslinked polymer, such as 10 to 40 wt % of the
monomer based on the total weight of the crosslinked polymer.
In certain aspects, the present disclosure provides a method of
making an orthodontic appliance comprising a crosslinked polymer,
the method comprising providing a curable composition described
herein; and fabricating the crosslinked polymer by a direct or
additive fabrication process. The composition may be exposed to
light in said direct or additive fabrication process. The process
may further comprise an additional curing step following
fabrication of the crosslinked polymer.
In certain aspects, the present disclosure provides an orthodontic
appliance comprising a crosslinked polymer described herein. The
orthodontic appliance may be an aligner, expander or spacer. In
some embodiments, the orthodontic appliance comprises a plurality
of tooth receiving cavities configured to reposition teeth from a
first configuration toward a second configuration. In some
embodiments, the orthodontic appliance is one of a plurality of
orthodontic appliances configured to reposition the teeth from an
initial configuration toward a target configuration, optionally
according to a treatment plan.
As used herein the terms "rigidity" and "stiffness" are used
interchangeably, as are the corresponding terms "rigid" and
"stiff."
As used herein a "plurality of teeth" encompasses two or more
teeth.
In many embodiments, one or more posterior teeth comprises one or
more of a molar, a premolar or a canine, and one or more anterior
teeth comprising one or more of a central incisor, a lateral
incisor, a cuspid, a first bicuspid or a second bicuspid.
The curable compositions and crosslinked polymers according to the
present disclosure exhibit favorable thermomechanical properties
for use as orthodontic appliances, for example, for moving one or
more teeth.
The embodiments disclosed herein can be used to couple groups of
one or more teeth to each other. The groups of one or more teeth
may comprise a first group of one or more anterior teeth and a
second group of one or more posterior teeth. The first group of
teeth can be coupled to the second group of teeth with the
polymeric shell appliances as disclosed herein.
The embodiments disclosed herein are well suited for moving one or
more teeth of the first group of one or more teeth or moving one or
more of the second group of one or more teeth, and combinations
thereof.
The embodiments disclosed herein are well suited for combination
with one or known commercially available tooth moving components
such as attachments and polymeric shell appliances. In many
embodiments, the appliance and one or more attachments are
configured to move one or more teeth along a tooth movement vector
comprising six degrees of freedom, in which three degrees of
freedom are rotational and three degrees of freedom are
translation.
The present disclosure provides orthodontic systems and related
methods for designing and providing improved or more effective
tooth moving systems for eliciting a desired tooth movement and/or
repositioning teeth into a desired arrangement.
Although reference is made to an appliance comprising a polymeric
shell appliance, the embodiments disclosed herein are well suited
for use with many appliances that receive teeth, for example
appliances without one or more of polymers or shells. The appliance
can be fabricated with one or more of many materials such as metal,
glass, reinforced fibers, carbon fiber, composites, reinforced
composites, aluminum, biological materials, and combinations
thereof for example. In some cases, the reinforced composites can
comprise a polymer matrix reinforced with ceramic or metallic
particles, for example. The appliance can be shaped in many ways,
such as with thermoforming or direct fabrication as described
herein, for example. Alternatively or in combination, the appliance
can be fabricated with machining such as an appliance fabricated
from a block of material with computer numeric control machining
Preferably, the appliance is fabricated using a curable composition
according to the present disclosure.
Turning now to the drawings, in which like numbers designate like
elements in the various figures, FIG. 1A illustrates an exemplary
tooth repositioning appliance or aligner 100 that can be worn by a
patient in order to achieve an incremental repositioning of
individual teeth 102 in the jaw. The appliance can include a shell
(e.g., a continuous polymeric shell or a segmented shell) having
teeth-receiving cavities that receive and resiliently reposition
the teeth. An appliance or portion(s) thereof may be indirectly
fabricated using a physical model of teeth. For example, an
appliance (e.g., polymeric appliance) can be formed using a
physical model of teeth and a sheet of suitable layers of polymeric
material. In some embodiments, a physical appliance is directly
fabricated, e.g., using rapid prototyping fabrication techniques,
from a digital model of an appliance. An appliance can fit over all
teeth present in an upper or lower jaw, or less than all of the
teeth. The appliance can be designed specifically to accommodate
the teeth of the patient (e.g., the topography of the
tooth-receiving cavities matches the topography of the patient's
teeth), and may be fabricated based on positive or negative models
of the patient's teeth generated by impression, scanning, and the
like. Alternatively, the appliance can be a generic appliance
configured to receive the teeth, but not necessarily shaped to
match the topography of the patient's teeth. In some cases, only
certain teeth received by an appliance will be repositioned by the
appliance while other teeth can provide a base or anchor region for
holding the appliance in place as it applies force against the
tooth or teeth targeted for repositioning. In some cases, some,
most, or even all of the teeth will be repositioned at some point
during treatment. Teeth that are moved can also serve as a base or
anchor for holding the appliance as it is worn by the patient.
Typically, no wires or other means will be provided for holding an
appliance in place over the teeth. In some cases, however, it may
be desirable or necessary to provide individual attachments or
other anchoring elements 104 on teeth 102 with corresponding
receptacles or apertures 106 in the appliance 100 so that the
appliance can apply a selected force on the tooth. Exemplary
appliances, including those utilized in the Invisalign.RTM. System,
are described in numerous patents and patent applications assigned
to Align Technology, Inc. including, for example, in U.S. Pat. Nos.
6,450,807, and 5,975,893, as well as on the company's website,
which is accessible on the World Wide Web (see, e.g., the url
"invisalign.com"). Examples of tooth-mounted attachments suitable
for use with orthodontic appliances are also described in patents
and patent applications assigned to Align Technology, Inc.,
including, for example, U.S. Pat. Nos. 6,309,215 and 6,830,450.
FIG. 1B illustrates a tooth repositioning system 110 including a
plurality of appliances 112, 114, 116. Any of the appliances
described herein can be designed and/or provided as part of a set
of a plurality of appliances used in a tooth repositioning system.
Each appliance may be configured so a tooth-receiving cavity has a
geometry corresponding to an intermediate or final tooth
arrangement intended for the appliance. The patient's teeth can be
progressively repositioned from an initial tooth arrangement to a
target tooth arrangement by placing a series of incremental
position adjustment appliances over the patient's teeth. For
example, the tooth repositioning system 110 can include a first
appliance 112 corresponding to an initial tooth arrangement, one or
more intermediate appliances 114 corresponding to one or more
intermediate arrangements, and a final appliance 116 corresponding
to a target arrangement. A target tooth arrangement can be a
planned final tooth arrangement selected for the patient's teeth at
the end of all planned orthodontic treatment. Alternatively, a
target arrangement can be one of some intermediate arrangements for
the patient's teeth during the course of orthodontic treatment,
which may include various different treatment scenarios, including,
but not limited to, instances where surgery is recommended, where
interproximal reduction (IPR) is appropriate, where a progress
check is scheduled, where anchor placement is best, where palatal
expansion is desirable, where restorative dentistry is involved
(e.g., inlays, onlays, crowns, bridges, implants, veneers, and the
like), etc. As such, it is understood that a target tooth
arrangement can be any planned resulting arrangement for the
patient's teeth that follows one or more incremental repositioning
stages. Likewise, an initial tooth arrangement can be any initial
arrangement for the patient's teeth that is followed by one or more
incremental repositioning stages.
FIG. 1C illustrates a method 150 of orthodontic treatment using a
plurality of appliances, in accordance with embodiments. The method
150 can be practiced using any of the appliances or appliance sets
described herein. In step 160, a first orthodontic appliance is
applied to a patient's teeth in order to reposition the teeth from
a first tooth arrangement to a second tooth arrangement. In step
170, a second orthodontic appliance is applied to the patient's
teeth in order to reposition the teeth from the second tooth
arrangement to a third tooth arrangement. The method 150 can be
repeated as necessary using any suitable number and combination of
sequential appliances in order to incrementally reposition the
patient's teeth from an initial arrangement to a target
arrangement. The appliances can be generated all at the same stage
or in sets or batches (e.g., at the beginning of a stage of the
treatment), or the appliances can be fabricated one at a time, and
the patient can wear each appliance until the pressure of each
appliance on the teeth can no longer be felt or until the maximum
amount of expressed tooth movement for that given stage has been
achieved. A plurality of different appliances (e.g., a set) can be
designed and even fabricated prior to the patient wearing any
appliance of the plurality. After wearing an appliance for an
appropriate period of time, the patient can replace the current
appliance with the next appliance in the series until no more
appliances remain. The appliances are generally not affixed to the
teeth and the patient may place and replace the appliances at any
time during the procedure (e.g., patient-removable appliances). The
final appliance or several appliances in the series may have a
geometry or geometries selected to overcorrect the tooth
arrangement. For instance, one or more appliances may have a
geometry that would (if fully achieved) move individual teeth
beyond the tooth arrangement that has been selected as the "final."
Such over-correction may be desirable in order to offset potential
relapse after the repositioning method has been terminated (e.g.,
permit movement of individual teeth back toward their pre-corrected
positions). Over-correction may also be beneficial to speed the
rate of correction (e.g., an appliance with a geometry that is
positioned beyond a desired intermediate or final position may
shift the individual teeth toward the position at a greater rate).
In such cases, the use of an appliance can be terminated before the
teeth reach the positions defined by the appliance. Furthermore,
over-correction may be deliberately applied in order to compensate
for any inaccuracies or limitations of the appliance.
The various embodiments of the orthodontic appliances presented
herein can be fabricated in a wide variety of ways. In some
embodiments, the orthodontic appliances herein (or portions
thereof) can be produced using direct fabrication, such as additive
manufacturing techniques (also referred to herein as "3D printing")
or subtractive manufacturing techniques (e.g., milling). In some
embodiments, direct fabrication involves forming an object (e.g.,
an orthodontic appliance or a portion thereof) without using a
physical template (e.g., mold, mask etc.) to define the object
geometry. Additive manufacturing techniques can be categorized as
follows: (1) vat photopolymerization (e.g., stereolithography), in
which an object is constructed layer by layer from a vat of liquid
photopolymer resin; (2) material jetting, in which material is
jetted onto a build platform using either a continuous or drop on
demand (DOD) approach; (3) binder jetting, in which alternating
layers of a build material (e.g., a powder-based material) and a
binding material (e.g., a liquid binder) are deposited by a print
head; (4) fused deposition modeling (FDM), in which material is
drawn though a nozzle, heated, and deposited layer by layer; (5)
powder bed fusion, including but not limited to direct metal laser
sintering (DMLS), electron beam melting (EBM), selective heat
sintering (SHS), selective laser melting (SLM), and selective laser
sintering (SLS); (6) sheet lamination, including but not limited to
laminated object manufacturing (LOM) and ultrasonic additive
manufacturing (UAM); and (7) directed energy deposition, including
but not limited to laser engineering net shaping, directed light
fabrication, direct metal deposition, and 3D laser cladding. For
example, stereolithography can be used to directly fabricate one or
more of the appliances herein. In some embodiments,
stereolithography involves selective polymerization of a
photosensitive resin (e.g., a photopolymer) according to a desired
cross-sectional shape using light (e.g., ultraviolet light). The
object geometry can be built up in a layer-by-layer fashion by
sequentially polymerizing a plurality of object cross-sections. As
another example, the appliances herein can be directly fabricated
using selective laser sintering. In some embodiments, selective
laser sintering involves using a laser beam to selectively melt and
fuse a layer of powdered material according to a desired
cross-sectional shape in order to build up the object geometry. As
yet another example, the appliances herein can be directly
fabricated by fused deposition modeling. In some embodiments, fused
deposition modeling involves melting and selectively depositing a
thin filament of thermoplastic polymer in a layer-by-layer manner
in order to form an object. In yet another example, material
jetting can be used to directly fabricate the appliances herein. In
some embodiments, material jetting involves jetting or extruding
one or more materials onto a build surface in order to form
successive layers of the object geometry.
Alternatively or in combination, some embodiments of the appliances
herein (or portions thereof) can be produced using indirect
fabrication techniques, such as by thermoforming over a positive or
negative mold. Indirect fabrication of an orthodontic appliance can
involve producing a positive or negative mold of the patient's
dentition in a target arrangement (e.g., by rapid prototyping,
milling, etc.) and thermoforming one or more sheets of material
over the mold in order to generate an appliance shell.
In some embodiments, the direct fabrication methods provided herein
build up the object geometry in a layer-by-layer fashion, with
successive layers being formed in discrete build steps.
Alternatively or in combination, direct fabrication methods that
allow for continuous build-up of an object geometry can be used,
referred to herein as "continuous direct fabrication." Various
types of continuous direct fabrication methods can be used. As an
example, in some embodiments, the appliances herein are fabricated
using "continuous liquid interphase printing," in which an object
is continuously built up from a reservoir of photopolymerizable
resin by forming a gradient of partially cured resin between the
building surface of the object and a polymerization-inhibited "dead
zone." In some embodiments, a semi-permeable membrane is used to
control transport of a photopolymerization inhibitor (e.g., oxygen)
into the dead zone in order to form the polymerization gradient.
Continuous liquid interphase printing can achieve fabrication
speeds about 25 times to about 100 times faster than other direct
fabrication methods, and speeds about 1000 times faster can be
achieved with the incorporation of cooling systems. Continuous
liquid interphase printing is described in U.S. Patent Publication
Nos. 2015/0097315, 2015/0097316, and 2015/0102532, the disclosures
of each of which are incorporated herein by reference in their
entirety.
As another example, a continuous direct fabrication method can
achieve continuous build-up of an object geometry by continuous
movement of the build platform (e.g., along the vertical or
Z-direction) during the irradiation phase, such that the hardening
depth of the irradiated photopolymer is controlled by the movement
speed. Accordingly, continuous polymerization of material on the
build surface can be achieved. Such methods are described in U.S.
Pat. No. 7,892,474, the disclosure of which is incorporated herein
by reference in its entirety.
In another example, a continuous direct fabrication method can
involve extruding a composite material composed of a curable liquid
material surrounding a solid strand. The composite material can be
extruded along a continuous three-dimensional path in order to form
the object. Such methods are described in U.S. Patent Publication
No. 2014/0061974, the disclosure of which is incorporated herein by
reference in its entirety.
In yet another example, a continuous direct fabrication method
utilizes a "heliolithography" approach in which the liquid
photopolymer is cured with focused radiation while the build
platform is continuously rotated and raised. Accordingly, the
object geometry can be continuously built up along a spiral build
path. Such methods are described in U.S. Patent Publication No.
2014/0265034, the disclosure of which is incorporated herein by
reference in its entirety.
The direct fabrication approaches provided herein are compatible
with a wide variety of materials, including but not limited to one
or more of the following: a polyester, a co-polyester, a
polycarbonate, a thermoplastic polyurethane, a polypropylene, a
polyethylene, a polypropylene and polyethylene copolymer, an
acrylic, a cyclic block copolymer, a polyetheretherketone, a
polyamide, a polyethylene terephthalate, a polybutylene
terephthalate, a polyetherimide, a polyethersulfone, a
polytrimethylene terephthalate, a styrenic block copolymer (SBC), a
silicone rubber, an elastomeric alloy, a thermoplastic elastomer
(TPE), a thermoplastic vulcanizate (TPV) elastomer, a polyurethane
elastomer, a block copolymer elastomer, a polyolefin blend
elastomer, a thermoplastic co-polyester elastomer, a thermoplastic
polyamide elastomer, a thermoset material, or combinations thereof.
The materials used for direct fabrication can be provided in an
uncured form (e.g., as a liquid, resin, powder, etc.) and can be
cured (e.g., by photopolymerization, light curing, gas curing,
laser curing, crosslinking, etc.) in order to form an orthodontic
appliance or a portion thereof. The properties of the material
before curing may differ from the properties of the material after
curing. Once cured, the materials herein can exhibit sufficient
strength, stiffness, durability, biocompatibility, etc. for use in
an orthodontic appliance. The post-curing properties of the
materials used can be selected according to the desired properties
for the corresponding portions of the appliance.
In some embodiments, relatively rigid portions of the orthodontic
appliance can be formed via direct fabrication using one or more of
the following materials: a polyester, a co-polyester, a
polycarbonate, a thermoplastic polyurethane, a polypropylene, a
polyethylene, a polypropylene and polyethylene copolymer, an
acrylic, a cyclic block copolymer, a polyetheretherketone, a
polyamide, a polyethylene terephthalate, a polybutylene
terephthalate, a polyetherimide, a polyethersulfone, and/or a
polytrimethylene terephthalate.
In some embodiments, relatively elastic portions of the orthodontic
appliance can be formed via direct fabrication using one or more of
the following materials: a styrenic block copolymer (SBC), a
silicone rubber, an elastomeric alloy, a thermoplastic elastomer
(TPE), a thermoplastic vulcanizate (TPV) elastomer, a polyurethane
elastomer, a block copolymer elastomer, a polyolefin blend
elastomer, a thermoplastic co-polyester elastomer, and/or a
thermoplastic polyamide elastomer.
Machine parameters can include curing parameters. For digital light
processing (DLP)-based curing systems, curing parameters can
include power, curing time, and/or grayscale of the full image. For
laser-based curing systems, curing parameters can include power,
speed, beam size, beam shape and/or power distribution of the beam.
For printing systems, curing parameters can include material drop
size, viscosity, and/or curing power. These machine parameters can
be monitored and adjusted on a regular basis (e.g., some parameters
at every 1-x layers and some parameters after each build) as part
of the process control on the fabrication machine. Process control
can be achieved by including a sensor on the machine that measures
power and other beam parameters every layer or every few seconds
and automatically adjusts them with a feedback loop. For DLP
machines, gray scale can be measured and calibrated before, during,
and/or at the end of each build, and/or at predetermined time
intervals (e.g., every n.sup.th build, once per hour, once per day,
once per week, etc.), depending on the stability of the system. In
addition, material properties and/or photo-characteristics can be
provided to the fabrication machine, and a machine process control
module can use these parameters to adjust machine parameters (e.g.,
power, time, gray scale, etc.) to compensate for variability in
material properties. By implementing process controls for the
fabrication machine, reduced variability in appliance accuracy and
residual stress can be achieved.
Optionally, the direct fabrication methods described herein allow
for fabrication of an appliance including multiple materials,
referred to herein as "multi-material direct fabrication." In some
embodiments, a multi-material direct fabrication method involves
concurrently forming an object from multiple materials in a single
manufacturing step. For instance, a multi-tip extrusion apparatus
can be used to selectively dispense multiple types of materials
from distinct material supply sources in order to fabricate an
object from a plurality of different materials. Such methods are
described in U.S. Pat. No. 6,749,414, the disclosure of which is
incorporated herein by reference in its entirety. Alternatively or
in combination, a multi-material direct fabrication method can
involve forming an object from multiple materials in a plurality of
sequential manufacturing steps. For instance, a first portion of
the object can be formed from a first material in accordance with
any of the direct fabrication methods herein, then a second portion
of the object can be formed from a second material in accordance
with methods herein, and so on, until the entirety of the object
has been formed.
Direct fabrication can provide various advantages compared to other
manufacturing approaches. For instance, in contrast to indirect
fabrication, direct fabrication permits production of an
orthodontic appliance without utilizing any molds or templates for
shaping the appliance, thus reducing the number of manufacturing
steps involved and improving the resolution and accuracy of the
final appliance geometry. Additionally, direct fabrication permits
precise control over the three-dimensional geometry of the
appliance, such as the appliance thickness. Complex structures
and/or auxiliary components can be formed integrally as a single
piece with the appliance shell in a single manufacturing step,
rather than being added to the shell in a separate manufacturing
step. In some embodiments, direct fabrication is used to produce
appliance geometries that would be difficult to create using
alternative manufacturing techniques, such as appliances with very
small or fine features, complex geometric shapes, undercuts,
interproximal structures, shells with variable thicknesses, and/or
internal structures (e.g., for improving strength with reduced
weight and material usage). For example, in some embodiments, the
direct fabrication approaches herein permit fabrication of an
orthodontic appliance with feature sizes of less than or equal to
about 5 .mu.m, or within a range from about 5 .mu.m to about 50
.mu.m, or within a range from about 20 .mu.m to about 50 .mu.m.
The direct fabrication techniques described herein can be used to
produce appliances with substantially isotropic material
properties, e.g., substantially the same or similar strengths along
all directions. In some embodiments, the direct fabrication
approaches herein permit production of an orthodontic appliance
with a strength that varies by no more than about 25%, about 20%,
about 15%, about 10%, about 5%, about 1%, or about 0.5% along all
directions. Additionally, the direct fabrication approaches herein
can be used to produce orthodontic appliances at a faster speed
compared to other manufacturing techniques. In some embodiments,
the direct fabrication approaches herein allow for production of an
orthodontic appliance in a time interval less than or equal to
about 1 hour, about 30 minutes, about 25 minutes, about 20 minutes,
about 15 minutes, about 10 minutes, about 5 minutes, about 4
minutes, about 3 minutes, about 2 minutes, about 1 minutes, or
about 30 seconds. Such manufacturing speeds allow for rapid
"chair-side" production of customized appliances, e.g., during a
routine appointment or checkup.
In some embodiments, the direct fabrication methods described
herein implement process controls for various machine parameters of
a direct fabrication system or device in order to ensure that the
resultant appliances are fabricated with a high degree of
precision. Such precision can be beneficial for ensuring accurate
delivery of a desired force system to the teeth in order to
effectively elicit tooth movements. Process controls can be
implemented to account for process variability arising from
multiple sources, such as the material properties, machine
parameters, environmental variables, and/or post-processing
parameters.
Material properties may vary depending on the properties of raw
materials, purity of raw materials, and/or process variables during
mixing of the raw materials. In many embodiments, resins or other
materials for direct fabrication should be manufactured with tight
process control to ensure little variability in
photo-characteristics, material properties (e.g., viscosity,
surface tension), physical properties (e.g., modulus, strength,
elongation) and/or thermal properties (e.g., glass transition
temperature, heat deflection temperature). Process control for a
material manufacturing process can be achieved with screening of
raw materials for physical properties and/or control of
temperature, humidity, and/or other process parameters during the
mixing process. By implementing process controls for the material
manufacturing procedure, reduced variability of process parameters
and more uniform material properties for each batch of material can
be achieved. Residual variability in material properties can be
compensated with process control on the machine, as discussed
further herein.
Machine parameters can include curing parameters. For digital light
processing (DLP)-based curing systems, curing parameters can
include power, curing time, and/or grayscale of the full image. For
laser-based curing systems, curing parameters can include power,
speed, beam size, beam shape and/or power distribution of the beam.
For printing systems, curing parameters can include material drop
size, viscosity, and/or curing power. These machine parameters can
be monitored and adjusted on a regular basis (e.g., some parameters
at every 1-x layers and some parameters after each build) as part
of the process control on the fabrication machine. Process control
can be achieved by including a sensor on the machine that measures
power and other beam parameters every layer or every few seconds
and automatically adjusts them with a feedback loop. For DLP
machines, gray scale can be measured and calibrated at the end of
each build. In addition, material properties and/or
photo-characteristics can be provided to the fabrication machine,
and a machine process control module can use these parameters to
adjust machine parameters (e.g., power, time, gray scale, etc.) to
compensate for variability in material properties. By implementing
process controls for the fabrication machine, reduced variability
in appliance accuracy and residual stress can be achieved.
In many embodiments, environmental variables (e.g., temperature,
humidity, Sunlight or exposure to other energy/curing source) are
maintained in a tight range to reduce variable in appliance
thickness and/or other properties. Optionally, machine parameters
can be adjusted to compensate for environmental variables.
In many embodiments, post-processing of appliances includes
cleaning, post-curing, and/or support removal processes. Relevant
post-processing parameters can include purity of cleaning agent,
cleaning pressure and/or temperature, cleaning time, post-curing
energy and/or time, and/or consistency of support removal process.
These parameters can be measured and adjusted as part of a process
control scheme. In addition, appliance physical properties can be
varied by modifying the post-processing parameters. Adjusting
post-processing machine parameters can provide another way to
compensate for variability in material properties and/or machine
properties.
The configuration of the orthodontic appliances herein can be
determined according to a treatment plan for a patient, e.g., a
treatment plan involving successive administration of a plurality
of appliances for incrementally repositioning teeth. Computer-based
treatment planning and/or appliance manufacturing methods can be
used in order to facilitate the design and fabrication of
appliances. For instance, one or more of the appliance components
described herein can be digitally designed and fabricated with the
aid of computer-controlled manufacturing devices (e.g., computer
numerical control (CNC) milling, computer-controlled rapid
prototyping such as 3D printing, etc.). The computer-based methods
presented herein can improve the accuracy, flexibility, and
convenience of appliance fabrication.
FIG. 2 illustrates a method 200 for designing an orthodontic
appliance to be produced by direct fabrication, in accordance with
embodiments. The method 200 can be applied to any embodiment of the
orthodontic appliances described herein. Some or all of the steps
of the method 200 can be performed by any suitable data processing
system or device, e.g., one or more processors configured with
suitable instructions.
In step 210, a movement path to move one or more teeth from an
initial arrangement to a target arrangement is determined. The
initial arrangement can be determined from a mold or a scan of the
patient's teeth or mouth tissue, e.g., using wax bites, direct
contact scanning, x-ray imaging, tomographic imaging, sonographic
imaging, and other techniques for obtaining information about the
position and structure of the teeth, jaws, gums and other
orthodontically relevant tissue. From the obtained data, a digital
data set can be derived that represents the initial (e.g.,
pretreatment) arrangement of the patient's teeth and other tissues.
Optionally, the initial digital data set is processed to segment
the tissue constituents from each other. For example, data
structures that digitally represent individual tooth crowns can be
produced. Advantageously, digital models of entire teeth can be
produced, including measured or extrapolated hidden surfaces and
root structures, as well as surrounding bone and soft tissue.
The target arrangement of the teeth (e.g., a desired and intended
end result of orthodontic treatment) can be received from a
clinician in the form of a prescription, can be calculated from
basic orthodontic principles, and/or can be extrapolated
computationally from a clinical prescription. With a specification
of the desired final positions of the teeth and a digital
representation of the teeth themselves, the final position and
surface geometry of each tooth can be specified to form a complete
model of the tooth arrangement at the desired end of treatment.
Having both an initial position and a target position for each
tooth, a movement path can be defined for the motion of each tooth.
In some embodiments, the movement paths are configured to move the
teeth in the quickest fashion with the least amount of
round-tripping to bring the teeth from their initial positions to
their desired target positions. The tooth paths can optionally be
segmented, and the segments can be calculated so that each tooth's
motion within a segment stays within threshold limits of linear and
rotational translation. In this way, the end points of each path
segment can constitute a clinically viable repositioning, and the
aggregate of segment end points can constitute a clinically viable
sequence of tooth positions, so that moving from one point to the
next in the sequence does not result in a collision of teeth.
In step 220, a force system to produce movement of the one or more
teeth along the movement path is determined. A force system can
include one or more forces and/or one or more torques. Different
force systems can result in different types of tooth movement, such
as tipping, translation, rotation, extrusion, intrusion, root
movement, etc. Biomechanical principles, modeling techniques, force
calculation/measurement techniques, and the like, including
knowledge and approaches commonly used in orthodontia, may be used
to determine the appropriate force system to be applied to the
tooth to accomplish the tooth movement. In determining the force
system to be applied, sources may be considered including
literature, force systems determined by experimentation or virtual
modeling, computer-based modeling, clinical experience,
minimization of unwanted forces, etc.
The determination of the force system can include constraints on
the allowable forces, such as allowable directions and magnitudes,
as well as desired motions to be brought about by the applied
forces. For example, in fabricating palatal expanders, different
movement strategies may be desired for different patients. For
example, the amount of force needed to separate the palate can
depend on the age of the patient, as very young patients may not
have a fully-formed suture. Thus, in juvenile patients and others
without fully-closed palatal sutures, palatal expansion can be
accomplished with lower force magnitudes. Slower palatal movement
can also aid in growing bone to fill the expanding suture. For
other patients, a more rapid expansion may be desired, which can be
achieved by applying larger forces. These requirements can be
incorporated as needed to choose the structure and materials of
appliances; for example, by choosing palatal expanders capable of
applying large forces for rupturing the palatal suture and/or
causing rapid expansion of the palate. Subsequent appliance stages
can be designed to apply different amounts of force, such as first
applying a large force to break the suture, and then applying
smaller forces to keep the suture separated or gradually expand the
palate and/or arch.
The determination of the force system can also include modeling of
the facial structure of the patient, such as the skeletal structure
of the jaw and palate. Scan data of the palate and arch, such as
Xray data or 3D optical scanning data, for example, can be used to
determine parameters of the skeletal and muscular system of the
patient's mouth, so as to determine forces sufficient to provide a
desired expansion of the palate and/or arch. In some embodiments,
the thickness and/or density of the mid-palatal suture may be
measured, or input by a treating professional. In other
embodiments, the treating professional can select an appropriate
treatment based on physiological characteristics of the patient.
For example, the properties of the palate may also be estimated
based on factors such as the patient's age--for example, young
juvenile patients will typically require lower forces to expand the
suture than older patients, as the suture has not yet fully
formed.
In step 230, an arch or palate expander design for an orthodontic
appliance configured to produce the force system is determined.
Determination of the arch or palate expander design, appliance
geometry, material composition, and/or properties can be performed
using a treatment or force application simulation environment. A
simulation environment can include, e.g., computer modeling
systems, biomechanical systems or apparatus, and the like.
Optionally, digital models of the appliance and/or teeth can be
produced, such as finite element models. The finite element models
can be created using computer program application software
available from a variety of vendors. For creating solid geometry
models, computer aided engineering (CAE) or computer aided design
(CAD) programs can be used, such as the AutoCAD.RTM. software
products available from Autodesk, Inc., of San Rafael, Calif. For
creating finite element models and analyzing them, program products
from a number of vendors can be used, including finite element
analysis packages from ANSYS, Inc., of Canonsburg, Pa., and
SIMULIA(Abaqus) software products from Dassault Systemes of
Waltham, Mass.
Optionally, one or more arch or palate expander designs can be
selected for testing or force modeling. As noted above, a desired
tooth movement, as well as a force system required or desired for
eliciting the desired tooth movement, can be identified. Using the
simulation environment, a candidate arch or palate expander design
can be analyzed or modeled for determination of an actual force
system resulting from use of the candidate appliance. One or more
modifications can optionally be made to a candidate appliance, and
force modeling can be further analyzed as described, e.g., in order
to iteratively determine an appliance design that produces the
desired force system.
In step 240, instructions for fabrication of the orthodontic
appliance incorporating the arch or palate expander design are
generated. The instructions can be configured to control a
fabrication system or device in order to produce the orthodontic
appliance with the specified arch or palate expander design. In
some embodiments, the instructions are configured for manufacturing
the orthodontic appliance using direct fabrication (e.g.,
stereolithography, selective laser sintering, fused deposition
modeling, 3D printing, continuous direct fabrication,
multi-material direct fabrication, etc.), in accordance with the
various methods presented herein. In alternative embodiments, the
instructions can be configured for indirect fabrication of the
appliance, e.g., by thermoforming.
Method 200 may comprise additional steps: 1) The upper arch and
palate of the patient is scanned intraorally to generate three
dimensional data of the palate and upper arch; 2) The three
dimensional shape profile of the appliance is determined to provide
a gap and teeth engagement structures as described herein.
Although the above steps show a method 200 of designing an
orthodontic appliance in accordance with some embodiments, a person
of ordinary skill in the art will recognize some variations based
on the teaching described herein. Some of the steps may comprise
sub-steps. Some of the steps may be repeated as often as desired.
One or more steps of the method 200 may be performed with any
suitable fabrication system or device, such as the embodiments
described herein. Some of the steps may be optional, and the order
of the steps can be varied as desired.
FIG. 3 illustrates a method 300 for digitally planning an
orthodontic treatment and/or design or fabrication of an appliance,
in accordance with embodiments. The method 300 can be applied to
any of the treatment procedures described herein and can be
performed by any suitable data processing system.
In step 310, a digital representation of a patient's teeth is
received. The digital representation can include surface topography
data for the patient's intraoral cavity (including teeth, gingival
tissues, etc.). The surface topography data can be generated by
directly scanning the intraoral cavity, a physical model (positive
or negative) of the intraoral cavity, or an impression of the
intraoral cavity, using a suitable scanning device (e.g., a
handheld scanner, desktop scanner, etc.).
In step 320, one or more treatment stages are generated based on
the digital representation of the teeth. The treatment stages can
be incremental repositioning stages of an orthodontic treatment
procedure designed to move one or more of the patient's teeth from
an initial tooth arrangement to a target arrangement. For example,
the treatment stages can be generated by determining the initial
tooth arrangement indicated by the digital representation,
determining a target tooth arrangement, and determining movement
paths of one or more teeth in the initial arrangement necessary to
achieve the target tooth arrangement. The movement path can be
optimized based on minimizing the total distance moved, preventing
collisions between teeth, avoiding tooth movements that are more
difficult to achieve, or any other suitable criteria.
In step 330, at least one orthodontic appliance is fabricated based
on the generated treatment stages. For example, a set of appliances
can be fabricated, each shaped according a tooth arrangement
specified by one of the treatment stages, such that the appliances
can be sequentially worn by the patient to incrementally reposition
the teeth from the initial arrangement to the target arrangement.
The appliance set may include one or more of the orthodontic
appliances described herein. The fabrication of the appliance may
involve creating a digital model of the appliance to be used as
input to a computer-controlled fabrication system. The appliance
can be formed using direct fabrication methods, indirect
fabrication methods, or combinations thereof, as desired.
In some instances, staging of various arrangements or treatment
stages may not be necessary for design and/or fabrication of an
appliance. As illustrated by the dashed line in FIG. 3, design
and/or fabrication of an orthodontic appliance, and perhaps a
particular orthodontic treatment, may include use of a
representation of the patient's teeth (e.g., receive a digital
representation of the patient's teeth 310), followed by design
and/or fabrication of an orthodontic appliance based on a
representation of the patient's teeth in the arrangement
represented by the received representation.
EXAMPLES
The following examples are given for the purpose of illustrating
various embodiments of the invention and are not meant to limit the
present disclosure in any fashion. The present examples, along with
the methods described herein are presently representative of
preferred embodiments, are exemplary, and are not intended as
limitations on the scope of the invention. Changes therein and
other uses which are encompassed within the spirit of the invention
as defined by the scope of the claims will occur to those skilled
in the art.
All chemicals were purchased from commercial sources and were used
without further purification, unless otherwise stated.
1H NMR spectra were recorded on a BRUKER AC-E-200 FT-NMR
spectrometer. The chemical shifts are reported in ppm (s: singlet,
d: doublet, t: triplet, q: quartet, m: multiplet). The solvent used
was deuterated chloroform (CDCl.sub.3, 99.5% deuteration). IR
spectra were recorded on a Perkin Elmer Spectrum 65 FT-IR
spectrometer.
Synthesis Example 1: Synthesis of Glass Transition Modifier
TGM1
##STR00027##
20 g of cyclohexanedimethanol (CHDM, M=144.21 g/mol, 0.139 mol)
were added to 200 ml of dimethylformamide and stirred until
complete dissolution at 60.degree. C. Then, 61.66 g isophorone
diisocyanate (IPDI, M=222.3 g/mol, 0.277 mol) were added to the
mixture. The reaction was monitored using ATR-IR spectroscopy and
was finished when the area of the NCO group absorption signal
(2275-2250 cm.sup.-1) in the IR spectra became constant (approx. 3
h). Then, 36.10 g of hydroxyethyl methacrylate (HEMA, M=130.14
g/mol, 0.277 mol) were added to the mixture together with 35 mg of
3,5-di-tert-butyl-4-hydroxytoluene (BHT) as an inhibitor (300 ppm)
and 58 mg of dibutyltin dilaurate (DBTDL) as a catalyst (500 ppm).
The solution was reacted until the signal of the NCO group
completely disappeared in the IR spectra. The solvent was distilled
off and the resulting colorless viscous liquid TGM1 was used
without further purification. .sup.1H NMR (CDCl.sub.3, 200 MHz,
.delta., ppm): 6.14 (d, 2H, 2.times.>C.dbd.CH.sub.2, cis), 5.61
(d, 2H, 2.times.>C.dbd.CH.sub.2, trans), 4.95-4.47 (m, 4H,
4.times.C--NH--), 4.32 (m, 8H,
2.times.--O--CH.sub.2--CH.sub.2--O--), 4.1-3.8 (m, 6H,
2.times.>CH--NH, 2.times.>CH--CH.sub.2--O), 3.2 (q, 1H,
NH--CH.sub.2--), 2.9 (m, 3H, NH--CH.sub.2--), 1.95 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.9-0.8 (m, 40H, >CH.sub.2,
>C--CH.sub.2, >CH--). IR.sub.neat (cm.sup.-1): 3325
(.nu..sub.N--H), 2950 (.nu..sub.C--H), 2923 (.nu..sub.C--H), 1703
(.nu..sub.C.dbd.O), 1637 (.nu..sub.C.dbd.C), 1527 (.delta..sub.NH),
1452 (.delta..sub.CH3), 1300 (.delta..sub.CH2), 1237
(.nu..sub.C--O), 1165 (.nu..sub.C--N), 1139 (.nu..sub.C--O--), 1037
(.delta..sub.>CH2), 891 (.gamma..sub.C.dbd.C).
Synthesis Example 2: Synthesis of Glass Transition Modifier
TGM2
##STR00028##
The preparation of TGM2 was similar to Synthesis Example 1, using
hexamethylene diisocyanate (HDI) as the reactive isocyanate
compound in the first step. The white, solid product TGM2 was
quenched in deionized water, filtered off and dried before use.
.sup.1H NMR (CDCl.sub.3, 200 MHz, .delta., ppm): 6.06 (d, 2H,
2.times.>C.dbd.CH.sub.2, cis), 5.52 (d, 2H,
2.times.>C.dbd.CH.sub.2, trans), 4.72 (s, 4H, 4.times.--NH--),
4.25 (m, 8H, 2.times.--O--CH.sub.2--CH.sub.2--O--), 3.84 (d, 4H,
2.times.>CH--CH.sub.2--O), 3.09 (m, 8H,
4.times.OCO--NH--CH.sub.2--), 1.88 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.8-0.8 (m, 26H, --CH.sub.2--,
>CH--). IR.sub.neat (cm.sup.-1): 3325 (.nu..sub.N--H), 2940
(.nu..sub.C--H), 2854 (.nu..sub.C--H), 1715 (.nu..sub.C.dbd.O),
1685 (.nu..sub.C.dbd.O), 1638 (.nu..sub.C.dbd.C), 1532
(.delta..sub.NH), 1441 (.delta..sub.CH2), 1342 (.delta..sub.CH2),
1260 (.nu..sub.C--O--), 1167 (.nu..sub.C--N), 1137
(.nu..sub.C--O--), 1061 (.delta..sub.>CH2), 944
(.gamma..sub.C.dbd.C).
Synthesis Example 3. Synthesis of Glass Transition Modifier
TGM3
##STR00029##
The preparation of TGM3 was similar to Synthesis Example 1, using
trimethylhexamethylene diisocyanate (TMDI) as the reactive
isocyanate compound in the first step. The white, solid product
TGM3 was quenched in deionized water, filtered off and dried before
use. .sup.1H NMR (CDCl.sub.3, 200 MHz, .delta., ppm): 6.07 (d, 2H,
2.times.>C.dbd.CH.sub.2, cis), 5.52 (d, 2H,
2.times.>C.dbd.CH.sub.2, trans), 4.95-4.55 (m, 4H,
4.times.C--NH--), 4.26 (m, 8H,
2.times.--O--CH.sub.2--CH.sub.2--O--), 3.95-3.75 (m, 4H,
2.times.>CH--CH.sub.2--O--), 3.2-2.8 (m, 8H, NH--CH.sub.2--),
1.88 (s, 6H, 2.times.CH.sub.2.dbd.C--CH.sub.3), 1.8-0.7 (m, 38H,
>CH.sub.2, --CH.sub.2--CH.sub.2--, CH--CH.sub.3>CH--).
IR.sub.neat (cm.sup.-1): 3335 (.nu..sub.N--H), 2928
(.nu..sub.C--H), 2865 (.nu..sub.C--H), 1695 (.nu..sub.C.dbd.O),
1640 (.nu..sub.C.dbd.C), 1529 (.delta..sub.NH), 1450
(.delta..sub.CH2), 1364 (.delta..sub.CH2), 1240 (.nu..sub.C--O),
1163 (.nu..sub.C--N), 1139 (.nu..sub.C--O), 1033
(.delta..sub.>CH2), 946 (.gamma..sub.C=C).
Synthesis Example 4: Synthesis of Glass Transition Modifier
TGM4
##STR00030##
The preparation was similar to Synthesis Example 1, using
hexanediol (HD) as the diol compound in the first step. The
colorless, viscous product TGM4 was quenched in deionized water,
filtered off and dried before use. .sup.1H NMR (CDCl.sub.3, 200
MHz, .delta., ppm): 6.07 (d, 2H, 2.times.>C.dbd.CH.sub.2, cis),
5.53 (d, 2H, 2.times.>C.dbd.CH.sub.2, trans), 4.72 (s, 4H,
4.times.--NH--), 4.25 (m, 8H,
2.times.--O--CH.sub.2--CH.sub.2--O--), 3.84 (d, 4H,
2.times.>CH--CH.sub.2--O), 3.09 (m, 8H,
4.times.OCO--NH--CH.sub.2--), 1.88 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.8-0.8 (m, 26H, --CH.sub.2--,
>CH--). IR.sub.neat (cm.sup.-1): 3330 (.nu..sub.N--H), 2952
(.nu..sub.C--H), 2861 (.nu..sub.C--H), 1691 (.nu..sub.C.dbd.O),
1636 (.nu..sub.C.dbd.C), 1529 (.delta..sub.NH), 1454
(.delta..sub.CH2), 1364 (.delta..sub.CH2), 1301 (.nu..sub.C--O),
1238 (.nu..sub.C--O), 1171 (.nu..sub.C--N), 1041 (.nu..sub.C--O),
946 (.gamma..sub.C=C).
Synthesis Example 5: Synthesis of Toughness Modifier TNM1
##STR00031##
40 g of UBE Eternacoll UM-90 (1/1) polycarbonate diol
(M.sub.avg=900 g/mol, 0.044 mol, 10 eq) were added to 200 ml of
dimethylformamide and the solution was stirred at 90.degree. C.
Then, 8.22 g of HDI (M=168.2 g/mol, 0.049 mol, 11 eq) and 25 mg of
dibutyltin dilaurate (500 ppm) were added to the flask and the
reaction was monitored via ATR-IR spectroscopy. After approximately
3 h, the isocyanate signal in the IR spectra remained constant. In
the second step of the reaction, 1.15 g of HEMA (M=130.14 g/mol,
0.0089 mol, 2 eq) and 15 mg of butylhydroxytoluene (300 ppm) were
added and the reaction was continued until the signal of the NCO
group had completely disappeared in the IR spectra (approx. 1 h).
Afterwards, water was added to precipitate the colorless solid
product TNM1 which was washed with deionized water and dried in
vacuo. .sup.1H NMR (CDCl.sub.3, 200 MHz, .delta., ppm): 6.10 (d,
2H, 2.times.>C.dbd.CH.sub.2, cis), 5.54 (d, 2H,
2.times.>C.dbd.CH.sub.2, trans), 4.69 (s, 22H, 22.times.--NH--),
4.27 (m, 8H, 2.times.--O--CH.sub.2--CH.sub.2--O--), 4.15-3.77 (m,
264H, O.dbd.CO--CH.sub.2--), 3.12 (q, 44H, 22.times.
OCO--NH--CH.sub.2--), 1.81 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.75-0.98 (m, 692H,
>CH.sub.2, --CH.sub.2--, >CH--). IR.sub.neat (cm.sup.-1):
3333 (.nu..sub.N--H), 2930 (.nu..sub.C--H), 2858 (.nu..sub.C--H),
1717 (.nu..sub.C.dbd.O), 1684 (.nu..sub.C.dbd.O), 1637
(.nu..sub.C.dbd.C), 1530 (.delta..sub.NH), 1454 (.delta..sub.CH3),
1318 (.delta..sub.CH2), 1243 (.nu..sub.C--O), 1167 (.nu..sub.C--N),
1131 (.nu..sub.C--O), 1045 (.delta..sub.>CH2), 951
(.gamma..sub.C=C). GPC: M.sub.n=13,170 Da; PDI=2.27
Synthesis Example 6: Synthesis of Toughness Modifier TNM2
##STR00032##
The preparation was similar to Synthesis Example 3, using UBE
Eternacoll UH-100 polycarbonate diol (M.sub.avg=1000 g/mol, 10 eq)
was used as reactant. The white solid product TNM2 was precipitated
with ethanol and dried in vacuo. .sup.1H NMR (CDCl.sub.3, 200 MHz,
.delta., ppm): 6.11 (d, 2H, 2.times.>C.dbd.CH.sub.2, cis), 5.56
(d, 2H, 2.times.>C.dbd.CH.sub.2, trans), 4.69 (s, 22H,
22.times.--NH--), 4.27 (m, 8H,
2.times.--O--CH.sub.2--CH.sub.2--O--), 4.16-3.96 (m, 284H,
O.dbd.C--O--CH.sub.2--), 3.12 (q, 44H,
22.times.OCO--NH--CH.sub.2--), 1.92 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.75-1.21 (m, 656H,
--CH.sub.2--). IR.sub.neat (cm.sup.-1): 3322 (.nu..sub.N--H), 2936
(.nu..sub.C--H), 2862 (.nu..sub.C--H), 1717 (.nu..sub.C.dbd.O),
1683 (.nu..sub.C.dbd.O), 1638 (.nu..sub.C.dbd.C), 1537
(.delta..sub.NH), 1455 (.delta..sub.CH3), 1319 (.delta..sub.CH2),
1245 (.nu..sub.C--O), 1167 (.nu..sub.C--N), 1139 (.nu..sub.C--O),
1044 (.delta.>.sub.CH2), 954 (.gamma..sub.C=C). GPC:
M.sub.n=14,899 Da; PDI=2.28
Synthesis Example 7: Synthesis of Toughness Modifier TNM3
##STR00033##
The preparation was similar to Synthesis Example 3, using BENEBiOL
NL1050B from Mitsubishi Chemical (M.sub.avg=1000 g/mol, 10 eq) as
the polycarbonate diol. At the end of the synthesis, the solvent
was distilled off and the colorless viscous liquid TNM3 was used
without further purification. .sup.1H NMR (CDCl.sub.3, 200 MHz,
.delta., ppm): 6.07 (d, 2H, 2.times.>C.dbd.CH.sub.2, cis), 5.50
(d, 2H, 2.times.>C.dbd.CH.sub.2, trans), 4.74 (s, 22H,
22.times.--NH--), 4.26 (m, 8H,
2.times.--O--CH.sub.2--CH.sub.2--O--), 4.14 (m, 184H,
O.dbd.C--O--CH.sub.2--), 3.93 (m, 156H, O.dbd.C--O--CH.sub.2--),
3.13 (m, 44H, 22.times.OCO--NH--CH.sub.2--), 1.88 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.75 (s, 260H, --(CH.sub.2),
1.51-1.20 (m, 88H, NH--CH.sub.2--(CH.sub.2).sub.4--CH.sub.2--NH),
0.98 (m, 250H>C--(CH.sub.3).sub.2). IR.sub.neat (cm.sup.-1):
3384 (.nu..sub.N--H), 2961 (.nu..sub.C--H), 2936 (.nu..sub.C--H),
2879 (.nu..sub.C--H), 1742 (.nu..sub.C.dbd.O), 1716
(.nu..sub.C.dbd.O), 1637 (.nu..sub.C.dbd.C), 1524 (.delta..sub.NH),
1455 (.delta..sub.CH3), 1403 (.delta..sub.CH2), 1319
(.delta..sub.CH2), 1235 (.nu..sub.C--O), 1168 (.nu..sub.C--N), 1139
(.nu..sub.C--O), 1027 (.delta..sub.>CH2), 944 (.gamma..sub.C=C).
GPC: M.sub.n=14,932 Da; PDI=2.13
Synthesis Example 8: Synthesis of Toughness Modifier TNM4
##STR00034##
The preparation was similar to Synthesis Example 3, using BENEBiOL
NL2050B from Mitsubishi Chemical (M.sub.avg=2000 g/mol, 5 eq) and
HDI (M=168.2 g/mol, 6 eq) were used in a 5/6 ratio to obtain a
final molecular weight of .about.15,000 g/mol. Finally, the solvent
was distilled off and the colorless viscous liquid TNM4 was used
without further purification. .sup.1H NMR (CDCl.sub.3, 200 MHz,
.delta., ppm): 6.09 (d, 2H, 2.times.>C.dbd.CH.sub.2, cis), 5.54
(d, 2H, 2.times.>C.dbd.CH.sub.2, trans), 4.66 (s, 12H,
12.times.--NH--), 4.25 (m, 8H,
2.times.--O--CH.sub.2--CH.sub.2--O--), 4.09 (m, 192H,
O.dbd.C--O--CH.sub.2--), 3.89 (m, 164H, O.dbd.C--O--CH.sub.2--),
3.10 (m, 24H, 12.times.OCO--NH--CH.sub.2--), 1.88 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.71 (s, 250H, --(CH.sub.2)--),
1.51-1.20 (m, 48H, NH--CH.sub.2--(CH.sub.2).sub.4--CH.sub.2--NH),
0.99 (m, 240H>C--(CH.sub.3).sub.2). IR.sub.neat (cm.sup.-1):
3372 (.nu..sub.N--H), 2960 (.nu..sub.C--H), 2912 (.nu..sub.C--H),
2880 (.nu..sub.C--H), 1730 (.nu..sub.C.dbd.O), 1716
(.nu..sub.C.dbd.O), 1635 (.nu..sub.C.dbd.C), 1520 (.delta..sub.NH),
1468 (.delta..sub.CH3), 1399 (.delta..sub.CH2), 1305
(.delta..sub.CH2), 1242 (.nu..sub.C--O), 1173 (.nu..sub.C--N), 1148
(.nu..sub.C--O), 1025 (.delta..sub.>CH2), 952 (.gamma..sub.C=C).
GPC: M.sub.n=12,940 Da; PDI=2.04
Synthesis Example 9: Synthesis of Toughness Modifier TNM5
##STR00035##
The preparation was similar to Synthesis Example 3, using BENEBiOL
NL1050B from Mitsubishi Chemical (M.sub.avg=1000 g/mol, 10 eq) as
the polycarbonate diol and isophorone diisocyanate (M=222.3 g/mol,
11 eq) in a 10/11 ratio to obtain a final molecular weight of
15,000 g/mol. The product TNM5 was precipitated and washed with
deionized water and dried in vacuo. .sup.1H NMR (CDCl.sub.3, 200
MHz, .delta., ppm): 6.15 (d, 2H, 2.times.>C.dbd.CH.sub.2, cis),
5.60 (d, 2H, 2.times.>C.dbd.CH.sub.2, trans), 4.82 (s, 11H,
11.times.>CH--NH--), 4.58 (s, 11H, 11.times.--CH.sub.2--NH--),
4.32 (t, 8H, 2.times.--O--CH.sub.2--CH.sub.2--O--), 4.24-3.86 (m,
250H, >CH--NH, --CH.sub.2--O), 3.28 (s, 6H, --CH.sub.2--NH--),
2.95 (m, 16H, --CH.sub.2--NH--), 1.97 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.9-0.8 (t, 645H, >CH.sub.2,
>C--CH.sub.3, >CH--). IR.sub.neat (cm.sup.-1): 3377
(.nu..sub.N--H), 2957 (.nu..sub.C--H), 2925 (.nu..sub.C--H), 2875
(.nu..sub.C--H), 1742 (.nu..sub.C.dbd.O), 1717 (.nu..sub.C.dbd.O),
1637 (.nu..sub.C.dbd.C), 1524 (.delta..sub.NH), 1455
(.delta..sub.CH3), 1403 (.delta..sub.CH2), 1319 (.delta..sub.CH2),
1234 (.nu..sub.C--O), 1168 (.nu..sub.C--N), 1131 (.nu..sub.C--O),
1027 (.delta..sub.>CH2), 944 (.gamma..sub.C=C). GPC:
M.sub.n=13,901 Da; PDI=2.15
Synthesis Example 10: Synthesis of Toughness Modifier TNM6
##STR00036## ##STR00037##
For this preparation, 2900 Da polytetrahydrofuran, isophorone
diisocyanate, UBE Eternacoll UM-90 (1/1) mixed cyclohexane
carbonate-hexamethylene carbonate diol and
2-hydroxyethylmethacrylate were used. First, the
isocyanoisophorone-urethane ethylmethacrylate compound, IUEM, was
synthesized by mixing 2.6 g of 2-hydroxyethyl methacrylate
(M=130.14 g/mol, 0.02 mol) and 4.45 g of isophorone diisocyanate
(M=222.3 g/mol, 0.02 mol) at 40.degree. C. for 2 h. The reaction
was monitored by using ATR-IR spectroscopy and .sup.1H NMR.
The TNM6-A precursor was synthesized by reacting 29 g of
polytetrahydrofuran (M.sub.avg=2900 g/mol, 0.01 mol) with 4.45 g of
isophorone diisocyanate (M=222.3 g/mol, 0.02 mol) at 90.degree. C.
under argon atmosphere. The reaction was monitored using ATR-IR
spectroscopy and was completed after approximately 3 h.
After TNM6-A was formed, 18 g of UBE Eternacoll UM-90 (1/1)
polycarbonate diol (M.sub.avg=900 g/mol, 0.02 mol) in 40 ml of
distilled chloroform were added to the mixture at 25.degree. C.,
and then the mixture was heated up to 60.degree. C. and 29 mg of
dibutyltin dilaurate (500 ppm) was added as a catalyst. The
reaction solution was stirred and the formation of TNM6-B was
evaluated by the disappearance of the isocyanate peaks in the
ATR-IR spectra (after approx. 3 h). When all the isocyanate had
reacted with the polycarbonate diol, 7.05 g of IUEM (2 eq) were
added to the mixture and reacted at 40.degree. C. Completeness was
determined by means of ATR-IR spectra. After evaporation of the
chloroform, 29 mg BHT inhibitor (500 ppm) were added and the
colorless viscous liquid product TNM6 was dried in vacuo. .sup.1H
NMR (CDCl.sub.3, 200 MHz, .delta., ppm): 6.09 (d, 2H,
2.times.>C.dbd.CH.sub.2, cis), 5.55 (d, 2H,
2.times.>C.dbd.CH.sub.2, trans), 4.78 (s, 4H, 4.times.CH--NH--),
4.52 (s, 4H, 4.times.CH.sub.2--NH--), 4.27 (m, 8H,
2.times.--O--CH.sub.2--CH.sub.2--O--), 4.08-3.73 (m, 54H,
O.dbd.C--O--CH.sub.2--),3.36 (s, 156H, --CH.sub.2--O--CH.sub.2--),
3.19 (s, 4H, 4.times.OCO--NH--CH<), 2.86 (s, 8H,
4.times.OCO--NH--CH.sub.2--), 1.90 (s, 6H,
2.times.CH.sub.2.dbd.C--CH.sub.3), 1.79-0.68 (m, 308H,
>CH.sub.2, --CH.sub.2--, >CH--, >CH--CH.sub.3).
IR.sub.neat (cm.sup.-1): 3329 (.nu..sub.N--H), 2942
(.nu..sub.C--H), 2855 (.nu..sub.C--H), 2796 (.nu..sub.C--H), 1743
(.nu..sub.C.dbd.O), 1720 (.nu..sub.C.dbd.O), 1639
(.nu..sub.C.dbd.C), 1529 (.delta..sub.NH), 1449 (.delta..sub.CH3),
1366 (.delta..sub.CH2), 1246 (.nu..sub.C--O), 1104 (.nu..sub.C--O),
1045 (.delta..sub.>CH2), 955 (.gamma..sub.C=C). GPC: M.sub.n:
6,434 Da; PDI=2.79
Synthesis Example 11: Synthesis of Reactive Diluent RD1
##STR00038##
5.55 g of menthyl salicylate (20 mmol) were placed in a 50 mL round
bottom flask together with 5.27 g methacrylic anhydride (34 mmol)
and 0.12 g 4-dimethylaminopyridine (1 mmol, DMAP). The flask was
purged with Ar, heated to 120.degree. C. (oil bath temperature) and
stirred for 24 h. The conversion was monitored by means of TLC. At
completion, residual methacrylic anhydride and by-products were
distilled off in vacuo. Then, the crude product was purified by
column chromatography (PE:EE=6:1) to give 5.67 g (83%) of RD1,
menthyl salicylate methacrylate, which was stabilized using 250 ppm
3,5-di-tert-butyl-4-hydroxytoluene (BHT). .sup.1H NMR (CDCl.sub.3,
200 MHz, .delta., ppm): 8.01 (d, 1H; Ar--H), 7.52 (t, 1H; Ar--H),
7.29 (t, 1H; Ar--H), 7.29 (d, 1H; Ar--H), 6.39 (d, 1H;
.dbd.CH.sub.2), 5.78 (d, 1H; .dbd.CH.sub.2), 4.87 (q, 1H; COO--CH),
2.08 (s, 3H; CH.sub.2.dbd.CH.sub.2--CH.sub.3), 1.93-1.00 (m, 9H)
0.84 (d, 6H; (CH.sub.2).sub.2--CH--(CH.sub.3).sub.2), 0.75 (d, 3H;
(CH.sub.2).sub.2--CH--CH.sub.3). APT-NMR (CDCl.sub.3, 50.3 MHz,
.delta., ppm): 165.7 (C4, CO), 164.2 (C4, CO), 150.6 (C4), 135.7
(C4), 133.4 (C1), 131.7 (C1), 128.9 (C4), 127.4 (C2), 125.9 (C1),
123.8 (C1), 74.9 (C1), 47.1 (C1), 40.8 (C2), 34.3 (C2), 31.4 (C1),
26.1 (C1), 23.3 (C2), 22.0 (C3), 20.8 (C3), 18.4 (C3), 16.1
(C3).
Example 1: Preparation of Curable Compositions
Curable compositions according to the present disclosure were
prepared by mixing the inventive Components A to C, optionally by
heating them and optionally by admixing further components selected
from another diluent and core-shell particles. The latter serve as
additional toughness modifiers, i.e. for further increasing the
toughness of the polymerizate obtained from the particular
composition. More specifically, in compositions (1) to (15), the
following components were mixed in the ranges given in Table 1
below.
TABLE-US-00001 TABLE 1 Compositions of curable compositions (1) to
(15) Compositional ranges Component (wt %) Component A: (first)
glass transition temperature 20-50 modifier, TGM Component B:
(first) toughness modifier, TNM 25-50 Component C: (first) reactive
diluent 10-40 Component A: second glass transition temperature 0-30
modifier, TGM Component B: second toughness modifier, TNM 0-50
Component C: second reactive diluent 0-15 Additional component:
core-shell particles 0-5
The compositions thus obtained were heated to a processing
temperature of 90.degree. C. or 110.degree. C., respectively, and
their shear viscosities at these temperatures were determined using
a modular compact rheometer MCR 300 from Anton Paar.
Subsequently, the compositions were each cured in a 3D printing
process using a Hot Lithography apparatus prototype from Cubicure
(Vienna, Austria), which was substantially configured as
schematically shown in FIG. 4. To this end, a curable composition
according to the first aspect of the present disclosure, as defined
in the following examples, was filled into the transparent material
vat of the apparatus shown in FIG. 4, which vat was heated at
90-110.degree. C. The building platform was heated at
90-110.degree. C., too, and lowered to establish holohedral contact
with the upper surface of the curable composition. By irradiating
the composition with 375 nm UV radiation using a diode laser from
Soliton, having an output power of 70 mW, which was controlled to
trace a predefined prototype design, and alternately raising the
building platform, the composition was cured layer by layer by a
photopolymerization process according to the second aspect of the
disclosure, resulting in a crosslinked polymer according to the
third aspect of the present disclosure.
Example 2: Preparation of Curable Compositions (1) to (3)
The following components were mixed in the proportions shown in
Tables 2 to 4 to give curable compositions (1) to (3):
TABLE-US-00002 TABLE 2 Composition of (1) Curable composition 1
Composition (wt %) Component Component A: glass transition 42.5
TGM1 modifier Component B: toughness modifier 50 TNM1 Component C:
reactive diluent 7.5 RD2* *RD2: triethylene glycol dimethacrylate
(TEGDMA), purchased from Sigma Aldrich
TABLE-US-00003 TABLE 3 Composition of (2) Curable composition 2
Composition (wt %) Component Component A: glass transition 34 TGM1
modifier Component B: toughness modifier 30 TNM1 Component C:
reactive diluent 1 30 RD1 Component C: reactive diluent 2 6 RD2
TABLE-US-00004 TABLE 4 Composition of (3) Curable composition 3
Composition (wt %) Component Component A: glass transition 39 TGM1
modifier Component B: toughness modifier 38 TNM2 Component C:
reactive diluent 1 15 RD1 Component C: reactive diluent 2 7 RD2
The following Table 5 lists the viscosities of curable compositions
(1) to (3) and most relevant properties of the crosslinked polymers
obtained therefrom using Hot Lithography as well as the desirable
ranges for each property.
The respective property values were determined using the following
methods:
shear viscosity: rheometer MCR 301 from Anton Paar, rheological
measurement in rotation mode (PP-25, 50 s-1, 50-115.degree. C.,
3.degree. C./min);
tensile properties: tensile testing machine RetroLine Z050 from
Zwick Roell;
thermo mechanical properties: DMA 2980 from TA Instruments, test
method: 3-point bending (from -50.degree. C. to 110.degree. C.,
3.degree. C./min, 1 Hz, 10 .mu.m amplitude, static force 0.5
N);
stress-relaxation properties: RSA-G2 from TA Instruments, test
method: 3-point bending, 2% strain);
tensile strength at yield: according to ISO 527-2 5B;
elongation at yield: according to ISO 527-2 5B;
elongation at break: according to ISO 527-2 5B, optionally at a
crosshead speed of 5 mm/min;
tensile modulus: according to ISO 527-2 5B;
T.sub.g (.degree. C.): tan .delta. peak;
storage modulus at 37.degree. C. (MPa): supra;
stress relaxation at 37.degree. C. and 100% RH (%): remaining load
after 2 h; and
stress relaxation at 37.degree. C. and 100% RH (MPa): remaining
load after 2 h.
TABLE-US-00005 TABLE 5 Results of Compositions (1) to (3) Property
Desirable Range (1) (2) (3) Viscosity of formulation 1 < x <
70 Pa s at 90.degree. C. 182 Pa s 16.0 Pa s 45 Pa s at 110.degree.
C. 68 Pa s 7.5 Pa s 16 Pa s Polymer 1 Polymer 2 Polymer 3 Tensile
Strength at Yield >25 MPa, 43.1 46.0 43.3 (MPa) preferably
>40 MPa Elongation at Yield (%) >5% 6 6 7 Elongation at Break
(%) >20%, 31.1 30 35.2 preferably >30% Tensile Modulus (MPa)
>800 MPa, 867 1050 943 preferably >1000 MPa T.sub.g (.degree.
C.) >90.degree. C., >120* 147 134 preferably >100.degree.
C. Storage Modulus (MPa) >750 MPa, 830 1330 1350 preferably
>1000 MPa Stress Relaxation (% of >20%, 35.6 40.4 37.3
initial load) preferably >35% Stress Relaxation (MPa) >2 MPa,
3.9 10.5 7.6 preferably .gtoreq.3 MPa *approximated (sample broke
at a temperature above 105.degree. C.)
Table 5 shows that the 3D-printed photopolymers obtained from
curable compositions (1) to (3) exhibited very good properties,
almost all of which fell into the desirable ranges and the majority
of which even fell into the preferable ranges. Particularly, each
of the three polymers showed a high tensile strength>40 MPa, a
high T.sub.g>120.degree. C., and a high elongation at
break>30%. The toughness modifiers TNM1 and TNM2 provided the
best strengthening effects of all tested toughness modifiers,
resulting in high elongations at break while maintaining high
tensile strengths and T.sub.g values. Due to the fairly high
viscosities of TNM1 and TNM2 (Mw>13 kDa), reactive diluents
(<10 wt %) were added to the formulations to obtain processable
formulations. By comparing (1) and (2), it can be seen that higher
amounts of reactive diluents yield better processable formulations
(having viscosities<20 Pas at 90.degree. C.), while maintaining
the required mechanical properties.
Example 3: Preparation of Curable Compositions (4) to (6)
The following components were mixed in the proportions shown in
Tables 6 to 8 to give curable compositions (4) to (6):
TABLE-US-00006 TABLE 6 Composition of (4) Curable composition 4
Composition (wt %) Component Component A: glass transition 24.5
TGM1 modifier Component B: toughness modifier 30 TNM1 Component C:
reactive diluent 1 40 RD1 Component C: reactive diluent 2 4.5
RD2
TABLE-US-00007 TABLE 7 Composition of (5) Curable composition 5
Composition (wt %) Component Component A: glass transition 42.5
TGM1 modifier Component B: toughness modifier 50 TNM2 Component C:
reactive diluent 7.5 RD2
TABLE-US-00008 TABLE 8 Composition of (6) Curable composition 6
Composition (wt %) Component Component A: glass transition 30.5
TGM1 modifier Component B: toughness modifier 50 TNM2 Component C:
reactive diluent 1 15 RD1 Component C: reactive diluent 2 4.5
RD2
The following Table 9 lists the viscosities of curable compositions
(4) to (6) and most relevant properties of the crosslinked polymers
obtained therefrom using Hot Lithography as well as the desirable
ranges for each property.
TABLE-US-00009 TABLE 9 Results of Compositions (4) to (6) Property
Desirable Range (4) (5) (6) Viscosity of formulation 1 < x <
70 Pa s at 90.degree. C. 13.4 Pa s 78.6 Pa s 55.6 Pa s at
110.degree. C. 4.3 Pa s 28.4 Pa s 21.4 Pa s Polymer 4 Polymer 5
Polymer 6 Tensile Strength at Yield >25 MPa, 26.4 35.5 36.3
(MPa) preferably >40 MPa Elongation at Yield (%) >5% 6 7 6
Elongation at Break (%) >20%, 58.7 42.6 81.6 peferably >30%
Tensile Modulus (MPa) >800 MPa, 601 519 481 preferably >1000
MPa T.sub.g (.degree. C.) >90.degree. C., 131 122 127 preferably
>100.degree. C. Storage Modulus (MPa) >750 MPa, 1140 805 780
preferably >1000 MPa Stress Relaxation (% of >20%, 22.3 24.1
24.7 initial load) preferably >35% Stress Relaxation (MPa) >2
MPa, 3.6 2.3 2.8 preferably .gtoreq.3 MPa
Table 9 shows that the photopolymers obtained from curable
compositions (4) to (6) yielded desirable values for tensile
strength, elongation at yield, storage modulus, and stress
relaxation, lower values for tensile modulus, and very good results
for elongation at break and T.sub.g. The polymers obtained
exhibited higher elongations at break when TNM2 was used instead of
TNM1, which is likely due to the more flexible aliphatic structures
compared to the more rigid cycloaliphatic moieties in TNM1 (cf.
compositions (1) and (5)). Moreover, higher amounts of reactive
diluents resulted in increased elongations at break, which can be
seen from a comparison between compositions (2) and (4). Both
strategies resulted in lower tensile strengths and moduli. However,
high amounts of TNM2 (Compositions (5) and (6)) complicated the
processing of the resins, possibly due to its higher viscosity.
Example 4: Preparation of Curable Compositions (7) and (8)
The following components were mixed in the proportions shown in
Tables 10 and 11 to give curable compositions (7) and (8):
TABLE-US-00010 TABLE 10 Composition of (7) Curable composition 7
Composition (wt %) Component Component A: glass transition 30 TGM1
modifier Component B: toughness modifier 40 TNM2 Component C:
reactive diluent 30 RD1
TABLE-US-00011 TABLE 11 Composition of (8) Composition Curable
composition 8 (wt %) Component Component A: glass transition
modifier 30 TGM1 Component B: toughness modifier 40 TNM2 Component
C: reactive diluent 30 RD1 Additional component: core-shell +5
Albidur EP XP* particles *Albidur EP XP powder (core-shell
particle) is commercially available from TEGO .RTM..
The following Table 12 lists the viscosities of curable
compositions (7) and (8) and most relevant properties of the
crosslinked polymers obtained therefrom using Hot Lithography as
well as the desirable ranges for each property.
TABLE-US-00012 TABLE 12 Results of Compositions (7) and (8)
Property Desirable Range (7) (8) Viscosity of formulation 1 < x
< 70 Pa s at 5.4 Pa s 7.8 Pa s 90.degree. C. at 110.degree. C.
1.9 Pa s 2.7 Pa s Polymer 7 Polymer 8 Tensile Strength at Yield
>25 MPa, 33.0 31.0 (MPa) preferably >40 MPa Elongation at
Yield (%) >5% 7 7 Elongation at Break (%) >20%, 47.1 65.2
peferably >30% Tensile Modulus (MPa) >800 MPa, 608 567
preferably >1000 MPa T.sub.g (.degree. C.) >90.degree. C.,
105 102 preferably >100.degree. C. Storage Modulus (MPa) >750
MPa, 1180 1070 preferably >1000 MPa Stress Relaxation (% of
>20%, 14.2 12.3 initial load) preferably >35% Stress
Relaxation (MPa) >2 MPa, 1.8 1.0 preferably .gtoreq.3 MPa
Table 12 shows that the presence of a relatively high proportion of
reactive diluent RD1 and the addition of Albidur XP powder as an
additional toughness modifier yielded desirable values for tensile
strength, elongations at yield and at break. However, the storage
modulus and the stress relaxation results were less desirable. The
addition of Albidur EP XP powder in (8) resulted in an increased
elongation at break of >65% compared to (7) without core-shell
particles (47%), while maintaining similar values for all other
mechanical properties
Example 5: Preparation of Curable Compositions (9) and (10)
The following components were mixed in the proportions shown in
Tables 13 and 14 to give curable compositions (9) and (10):
TABLE-US-00013 TABLE 13 Composition of (9) Curable composition 9
Composition (wt %) Component Component A: glass transition 42.5
TGM1 modifier Component B: toughness modifier 35 TNM5 Component C:
reactive diluent 22.5 RD2
TABLE-US-00014 TABLE 14 Composition of (10) Curable composition 10
Composition (wt %) Component Component A: glass transition 30 TGM1
modifier Component B: toughness modifier 40 TNM5 Component C:
reactive diluent 1 13 RD1 Component C: reactive diluent 2 17
RD2
The following Table 15 lists the viscosities of curable
compositions (9) and (10) and most relevant properties of the
crosslinked polymers obtained therefrom using Hot Lithography as
well as the desirable ranges for each property.
TABLE-US-00015 TABLE 15 Results of Compositions (9) and (10)
Property Desirable Range (9) (10) Viscosity of formulation 1 < x
< 70 Pa s at 6.3 Pa s 8.5 Pa s 90.degree. C. at 110.degree. C.
1.9 Pa s 2.6 Pa s Polymer Polymer 9 10 Tensile Strength at Yield
>25 MPa, 78.9 66.0 (MPa) preferably >40 MPa Elongation at
Yield (%) >5% --* 7 Elongation at Break (%) >20%, 7.6 14.6
peferably >30% Tensile Modulus (MPa) >800 MPa, 1740 1530
preferably >1000 MPa T.sub.g (.degree. C.) >90.degree. C.,
125 113 preferably >100.degree. C. Storage Modulus (MPa) >750
MPa, 2540 2600 preferably >1000 MPa Stress Relaxation (% of
>20%, 9.2 3.6 initial load) preferably >35% Stress Relaxation
(MPa) >2 MPa, 7.5 3.0 preferably .gtoreq.3 MPa *sample broke
before reaching the yield point
Table 15 shows that the polymers obtained from compositions (9) and
(10) yielded excellent results for most of the properties listed,
except for elongation at break and stress relaxation. Without
wishing to be bound by theory, the inventors suppose that this was
because of the higher contents of rigid cycloaliphatic structures
(originating from isophorone diisocyanate) of TNM5 compared to TNM1
and TNM2.
Example 6: Preparation of Curable Compositions (11) and (12)
The following components were mixed in the proportions shown in
Tables 16 and 17 to give curable compositions (11) and (12):
TABLE-US-00016 TABLE 16 Composition of (11) Curable composition 11
Composition (wt %) Component Component A: glass transition 23 TGM1
modifier Component B: toughness modifier 47 TNM3 Component C:
reactive diluent 30 RD1
TABLE-US-00017 TABLE 17 Composition of (12) Curable composition 12
Composition (wt %) Component Component A: glass transition 23 TGM1
modifier Component B: toughness modifier 47 TNM4 Component C:
reactive diluent 30 RD1
The following Table 18 lists the viscosities of curable
compositions (11) and (12) and most relevant properties of the
crosslinked polymers obtained therefrom using Hot Lithography as
well as the desirable ranges for each property.
TABLE-US-00018 TABLE 18 Results of Compositions (11) and (12)
Property Desirable Range (11) (12) Viscosity of formulation 1 <
x < 70 Pa s at 9.2 Pa s 7.1 Pa s 90.degree. C. at 110.degree. C.
2.1 Pa s 2.0 Pa s Polymer Polymer 11 12 Tensile Strength at Yield
>25 MPa, 28.3 24.1 (MPa) preferably >40 MPa Elongation at
Yield (%) >5% 8 7 Elongation at Break (%) >20%, 77.9 80.5
peferably >30% Tensile Modulus (MPa) >800 MPa, 541 389
preferably >1000 MPa T.sub.g (.degree. C.) >90.degree. C.,
107 111 preferably >100.degree. C. Storage Modulus (MPa) >750
MPa, 1110 1010 preferably >1000 MPa Stress Relaxation (% of
>20%, 9.7 12.8 initial load) preferably >35% Stress
Relaxation (MPa) >2 MPa, 0.79 1.24 preferably .gtoreq.3 MPa
Table 18 shows that the compositions of (11) and (12) resulted in
polymers exhibiting desirable values for tensile strength,
elongation at yield and at break, T.sub.g, and storage modulus, but
less desirable values for tensile modulus and stress relaxation. It
further shows that exchanging toughness modifier TNM3 used in (11)
for TNM4 in (12), thereby approximately doubling the chain length
of the polycarbonate diol based on 2,2-dimethyl-1,3-propanediol,
but maintaining the proportions of the Components A to C, resulted
in polymer properties comparable to those of (11). As expected, the
elongation at break outperforms those of (1) to (3). Without
wishing to be bound by theory, the inventors suppose that the
reason why the values for tensile strength, tensile modulus and
T.sub.g did not reach the preferred ranges was that there are no
rigid cycloaliphatic structures present in TNM3 and TNM4.
Example 7: Preparation of Curable Composition (13)
The following components were mixed in the proportions shown in
Table 19 to give curable composition (13):
TABLE-US-00019 TABLE 19 Composition of (13) Curable composition 13
Composition (wt %) Component Component A: glass transition 28 TGM1
modifier Component B: toughness modifier 67 TNM6 Component C:
reactive diluent 5 RD1
The following Table 20 lists the viscosity of curable composition
(13) and most relevant properties of the crosslinked polymer
obtained therefrom using Hot Lithography as well as the desirable
ranges for each property.
TABLE-US-00020 TABLE 20 Results of Composition (13) Property
Desirable Range (13) Viscosity of formulation 1 < x < 70 Pa s
at 90.degree. C. 37.0 Pa s at 110.degree. C. 12.2 Pa s Polymer 13
Tensile Strength at Yield >25 MPa, 18.0 (MPa) preferably >40
MPa Elongation at Yield (%) >5% 9 Elongation at Break (%)
>20%, 16.3 peferably >30% Tensile Modulus (MPa) >800 MPa,
246 preferably >1000 MPa T.sub.g (.degree. C.) >90.degree.
C., 146 preferably >100.degree. C. Storage Modulus (MPa) >750
MPa, 495 preferably >1000 MPa Stress Relaxation (% of >20%,
n.d. initial load) preferably >35% Stress Relaxation (MPa) >2
MPa, n.d. preferably .gtoreq.3 MPa n.d.: not determined
Table 20 shows that the photopolymer obtained from composition (13)
had a very high glass transition temperature, T.sub.g, and the
highest elongation at yield of all polymers obtained. Otherwise,
however, the measured values were less favorable. Without wishing
to be bound by theory, the inventors suppose that this was because
of both the relatively low molecular weight of <7 kDa of TNM6
and its unpreferably high proportion (67%) in the curable
composition.
Example 8: Evaluation of Curable Compositions and Crosslinked
Polymers Resulting Therefrom
FIGS. 5 to 7 show the measurement results obtained by testing the
curable compositions or the crosslinked polymers resulting
therefrom, respectively, of (1) to (10) for their viscosities (Pas)
and storage moduli (GPa) at varying temperatures (.degree. C.) as
well as their tensile strengths (N/mm.sup.2) at varying strains
(%). These diagrams show that all ten examples yielded curable
compositions which were well processible at processing temperatures
of 90.degree. C. or 110.degree. C. and which resulted in
crosslinked polymers having preferable storage moduli at 37.degree.
C. (i.e. body temperature) equal to or higher than 0.8 GPa, i.e.
800 MPa, and preferable tensile strengths at yield equal to or
higher than 25 N/mm.sup.2, i.e. 25 MPa. The majority of the
specimens even fell into the more preferable ranges of a storage
modulus at 37.degree. C. equal to or higher than 1 GPa, i.e. 1000
MPa, and a tensile strength at yield equal to or higher than 40
N/mm.sup.2, i.e. 40 MPa.
On the following pages, the proportions of the Components A to C of
curable compositions (1) to (13) are summarized in Table 21, and in
Table 22, the properties of all the polymers obtained by
3D-printing of these curable compositions are summarized.
TABLE-US-00021 TABLE 21 Summary of the compositions of curable
compositions (1) to (13) Comp. (1) (2) (3) (4) (5) (6) (7) (8) (9)
(10) (11) (12) (13) A 42.5% 34% 39% 24.5% 42.5% 30.5% 30% 30% 42.5%
30% 23% 23% 28% TGM1 TGM1 TGM1 TGM1 TGM1 TGM1 TGM1 TGM1 TGM1 TGM1
TGM1 TGM1 TGM1 B 50% 30% 38% 30% 50% 50% 40% 40% 35% 40% 47% 47%
67% TNM1 TNM1 TNM1 TNM1 TNM2 TNM2 TNM2 TNM2 TNM5 TNM5 TNM3 TNM4
TNM6 C 7.5% 30% 15% 40% 7.5% 15% 30% 30% 22.5% 13% 30% 30% 5% RD2
RD1 RD1 RD1 RD2 RD1 RD1 RD1 RD2 RD1 RD1 RD1 RD1 6% 7% 4.5% 4.5% 17%
RD2 RD2 RD2 RD2 RD2 CSP -- -- -- -- -- -- -- +5% -- -- -- -- --
CSP: core-shell particles All percentages are given in wt %, based
on 100 wt % of Components A to C.
TABLE-US-00022 TABLE 22 Summary of the properties of crosslinked
polymers obtained from (1) to (13) Prop. Ranges 1 2 3 4 5 6 7 8 9
10 11 12 13 T.S.Y. >25 43.1 46 43.3 26.4 35.5 36.3 33 31 78.9 66
28.3 24.1 18 (MPa) >40 E.Y. >5 6 6 7 6 7 6 7 7 n.d. 7 8 7 9
(%) >6 E.B. >20 31.1 30 35.2 58.7 42.6 81.6 47.1 65.2 7.6
14.6 77.9 80.5 16.3 (%) >30 T.M. >800 867 1050 943 601 519
481 608 567 1740 1530 541 389 246 (MPa) >1000 T.sub.g >90
>120 147 134 131 122 127 105 102 125 113 107 111 146 (.degree.
C.) >100 S.M. >750 830 1330 1350 1140 805 780 1180 1070 2540
2600 1110 1010 495 (MPa) >1000 S.R.1 >20 35.6 40.4 37.3 22.3
24.1 24.7 14.2 12.3 9.2 3.6 9.7 12.8 n.d. (%) >35 S.R.2 >2
3.9 10.5 7.6 3.6 2.3 2.8 1.8 1 7.5 3 0.79 1.24 n.d. (MPa) .gtoreq.3
T.S.Y.: tensile strength at yield (MPa) E.Y.: elongation at yield
(%) E.B.: elongation at break (%) T.M.: tensile modulus (MPa)
T.sub.g: glass transition temperature (.degree. C.) S.M.: storage
modulus (MPa) S.R.1: stress relaxation (% of initial load) S.R.2:
stress relaxation (MPa) The highest values of all examples for the
respective properties are underlined.
From the summaries in Tables 21 and 22, it can be seen that (1) to
(3) yielded the best results, since all properties fell into the
desired ranges, and almost all ((1) and (3)) or actually all ((2))
measured values even fell into the preferred ranges. Additionally,
the best performing polymer (2) even showed the highest values
among all examples for T.sub.g (147.degree. C.) and stress
relaxation (40.4% of the initial load and 10.2 MPa,
respectively).
In view of the proportions of the Components A to C in the curable
composition of (2), i.e. 34 wt % of Component A (TGM1), 30 wt % of
Component B (TNM1), and 36 wt % in total of Component C, being the
sum of 30 wt % of RD1 and 6 wt % of RD2, and (3), i.e. 39 wt % of
Component A (TGM1), 38 wt % of Component B (TNM1), and 22 wt % in
total of Component C, being the sum of 15 wt % of RD1 and 7 wt % of
RD2, as shown in Table 21, a skilled person may deduce that, for
obtaining optimal results, it is desirable to find a well-balanced
ratio of all three components and that Component A provides for
high T.sub.g and strength values at the expense of elongation at
break. Component B provides for high elongation at break and
toughness via strengthening effects, but it is difficult to process
high amounts thereof in the curable composition, and Component C
improves the processability of the formulations, particularly of
those comprising high amounts of high molecular weight toughness
modifiers, while maintaining high values for strength and
T.sub.g.
Additionally, comparing the results of (3), (8) and (10) to (12),
where the toughness modifiers TNM1 to TNM5 were used in roughly
comparable amounts, one may conclude that TNM1, TNM2 and TNM5, each
comprising a linear C.sub.6 (hexamethylene) and/or a cyclic C.sub.8
(cyclohexanedimethylene) radical R.sub.4 in the polycarbonate
blocks, the longest chain of which comprises 6 carbon atoms are to
be preferred over TNM3 and TNM4, each comprising a relatively
short-chained radical R.sub.4 (i.e. 2,2-dimethylpropylene the
longest chain of which has only 3 carbon atoms). Moreover, TNM1 and
TNM2 are to be preferred over the rather rigid TNM5, which yielded
less desirable results for toughness and elongation at break.
Therefrom, a skilled person may conclude that the rigid
cycloaliphatic moieties preferably originate from the polycarbonate
diol, rather than from the diisocyanate, since steric effects may
disturb the expected strengthening effects of the urea groups.
Further, from the results of (13), one may deduce that
polyether-modified toughness modifiers such as TNM6, or at least
excessively high proportions of such modifiers having relatively
low molecular weights in the curable composition, are less
preferable with regard to the mechanical properties of the
polymers, even though the glass transition temperature obtained in
(13) reached the second highest value among all polymers produced
(146.degree. C.).
Nonetheless, each of the crosslinked polymers obtained according
the present disclosure yielded at least two (12) or at least four
((10) and (11)) preferred values, which shows that the curable
compositions according to the present disclosure are highly
suitable for use in a high temperature lithography-based
photopolymerization process for producing crosslinked polymers
having desirable properties. Polymers of the present disclosure
thus produced, especially when used as orthodontic appliances, are
able to outmatch currently available materials in several respects,
particularly in terms of their thermomechanical properties and
manufacturing costs.
Example 9: Preparation of Curable Compositions (14) and (15)
The following components were mixed in the proportions shown in
Tables 23 and 24 to give curable compositions (14) and (15):
TABLE-US-00023 TABLE 23 Composition of (14) Curable composition 14
Composition (wt %) Component Component A: glass transition 30 TGM4
modifier Component B: toughness modifier 49 TNM2 Component C:
reactive diluent 1 21 RD1
TABLE-US-00024 TABLE 24 Composition of (15) Curable composition 15
Composition (wt %) Component Component A: glass transition 30 TGM4
modifier Component B: toughness modifier 49 TNM1 Component C:
reactive diluent 21 RD2
The following Table 25 lists the viscosities of curable
compositions (14) and (15) and most relevant properties of the
crosslinked polymers obtained therefrom using Hot Lithography as
well as the desirable ranges for each property.
TABLE-US-00025 TABLE 25 Results of Compositions 14 and 15 Property
Desirable Range (14) (15) Viscosity of formulation 1 < x < 70
Pa s at 56.0 Pa s 13.0 Pa s 90.degree. C. at 110.degree. C. 21.5 Pa
s 5.0 Pa s Polymer Polymer 14 15 Tensile Strength at Yield >25
MPa, 5.6 26.2 (MPa) preferably >40 MPa Elongation at Yield (%)
>5% 6.3 8.3 Elongation at Break (%) >20%, 205 98 preferably
>30% Tensile Modulus (MPa) >800 MPa, 154 552 preferably
>1000 MPa T.sub.g (.degree. C.) >90.degree. C., 101 107
preferably >100.degree. C. Storage Modulus (MPa) >750 MPa,
334 886 preferably >1000 MPa Stress Relaxation (% of >20%,
6.4 24.1 initial load) preferably >35% Stress Relaxation (MPa)
>2 MPa, 0.07 2.68 preferably .gtoreq.3 MPa
Table 25 shows that the photopolymers obtained from (14) and (15)
yielded good values for elongation at yield, elongation at break
and T.sub.g. The polymers obtained exhibited higher elongations at
break when TGM4 was used instead of TGM1, (cf. (1) to (13)).
However, the tensile strength, storage modulus and stress
relaxation results of the TNM2 containing example were less
desirable. Without wishing to be bound by theory, the inventors
suppose that the reason for this performance is the lower rigidity
of the system. By using TNM1, the formulation yielded desirable
results also in the tensile strength at yield and the stress
relaxation properties. Both examples showed low tensile
modulus.
Example 10: Preparation of Curable Compositions (16) to (22)
The following components were mixed in the proportions shown in
Tables 26 to give curable compositions (16) to (22):
TABLE-US-00026 TABLE 26 Compositions (16) to (22) Glass transition
Toughness Reactive Reactive Photo- Comp. modifier.sup.1
modifier.sup.2 Diluent.sup.3 Diluent.sup.4 Additive.s- up.5
Additive.sup.6 initiator.sup.7 No. (wt %) (wt %) (wt %) (wt %) (wt
%) (wt %) (wt %) 16 15 31.5 40 13.5 1 -- 0.4 17 15 31.5 40 13.5 1
-- 1 18 15 31.5 40 13.5 0.5 0.5 0.4 19 15 31.5 40 13.5 0.5 0.5 1 20
15 31.5 40 13.5 -- -- 1 21 15 31.4 40 13.5 -- 1 1 22 15 31.5 40
13.5 -- 3 1 .sup.1TGM1-RD1 (TGM1 with 30 wt % TEGDMA); .sup.2TNM2;
.sup.3HSMA; .sup.4triethylene glycol dimethacrylate; .sup.5BYK
.RTM.-430; .sup.6BYK .RTM.-A535; .sup.7TPO-L
BYK.RTM.-430 is a solution of a high molecular weight,
urea-modified, medium-polarity polyamides. Other high molecular
weight, urea-modified, medium-polarity polyamides are envisioned to
work in a comparable manner. BYK.RTM.-A535 is a silicone-free
solution that destroys foam polymers. Other defoamers are
envisioned to work in a comparable manner. Speedcure TPO-L from
Lambson (Ethyl (2,4,6-trimethylbenzoyl)phenyl phospinate) is a
photoinitiator that absorbs at 380 nm. Other photoinitiators are
envisioned, as are photoinitiators absorbing at other wavelengths.
The following Table 27 provides relevant properties of the
crosslinked polymers obtained from curable compositions (16) to
(22) using Hot Lithography, as well as desirable ranges for each
property.
The respective property values of Compositions 16 to 62 were
determined using the following methods:
tensile strength at yield: according to ASTM D1708;
elongation at break: according to ASTM D1708, optionally at a
crosshead speed of 1.7 mm/min;
tensile strength: according to ASTM D1708; and
Young's modulus: according to ASTM D1708.
TABLE-US-00027 TABLE 27 Results of Compositions 16 to 22 Property
Desirable Range P16 P17 P18 P19 P20 P21 P22 Tensile Strength at
Yield >25 MPa, 35 34 35 35 37 35 33 (MPa) preferably >40 MPa
Elongation at Break (%) >20%, 47.1 34.6 44.7 38.4 35.2 34.7 20.9
preferably >30% Tensile Strength (MPa) >25 MPa, 40 36 40 40
42 40 35 preferably >40 MPa Young's Modulus (MPa) >900 MPa,
991 1110 988 1064 1195 1136 1088 preferably >1100 MPa
Table 27 shows that each of compositions 16-22 had a tensile
strength at yield within the desirable range. Likewise,
compositions 16-21 had elongation at break values that are within
the preferred range, though composition 22 had an elongation at
break value that is at the low end of the desirable range. Without
wishing to be bound by theory, it is hypothesized the addition of
excess additive BYK.RTM.-A535 could have interfered with the
formation of a fully cohesive structure. In comparison, composition
21 has a three-fold decrease in the amount of BYK.RTM.-A535 and had
characteristics within the preferred range (elongation at break of
34.7%). The composition with the highest tensile strength at yield
and maximum tensile strength was P20, which is the composition that
did not have any added additives. However, compositions P16-P19 had
improved values for elongation at break over P20. P16 and P17
differed in the amount of photoinitiator (0.4 wt % and 1 wt %,
respectively), and Table 27 indicates a smaller amount of
photoinitiator may improve elongation at break values. A comparison
of P18 and P19 provides a similar indication.
Example 11: Preparation of Curable Compositions (23) to (33)
The following components were mixed in the proportions shown in
Table 28 to give curable compositions (23) to (29):
TABLE-US-00028 TABLE 28 Compositions (23) to (29) Toughness
Reactive Comp. Crosslinker.sup.1 Crosslinker.sup.2
Crosslinker.sup.3 modifier.sup.4- Diluent.sup.5 Additive.sup.6 No.
(wt %) (wt %) (wt %) (wt %) (wt %) (wt %) 23 -- -- 45 45 10 -- 24
-- -- 25 45 30 -- 25 -- -- 15 45 40 -- 26 -- -- 14.2 43 38 4.8 27
-- -- 12 45 38 5 28 15 -- -- 45 40 -- 29 -- 20 10 45 25 --
.sup.1TGM1-D4MA (TGM1 with 15 wt % D4MA); .sup.2H1188;
.sup.3TGM1-RD1 (TGM1 with 30 wt % TEGDMA); .sup.4TNM2-RD1 (TNM2
with 30 wt % RD1); .sup.5HSMA; .sup.6BDT1006
BDT1006 refers to Bomar.TM. BDT-1006, which is a hyperbranched
dendritic acrylate oligomer having an average acrylate
functionality of 6 groups per molecule. Other acrylate oligomers
are envisioned as additives. Other branched dendritic oligomers
having a plurality of functional groups are also envisioned as
additives. To each of these compositions was added TPO-L as a
photoinitiator (1 wt %). To P26 and P27 was added 0.25 and 0.2 wt %
2,2'-dihydroxy-4-methoxybenzophenone, respectively, as a
UV-blocker. The following Table 29 provides relevant properties of
the crosslinked polymers obtained from curable compositions (23) to
(29) using Hot Lithography.
TABLE-US-00029 TABLE 29 Results of Compositions 23 to 29 Desirable
Property Range P23 P24 P25 P26 P27 P28 P29 Stress Relaxation of
>20%, 11.07 11.15 23.33 16.75 20.00 15.92 20.24 Initial Load (%)
preferably >35% Elongation at Break (%) >20%, 20.5 15.5 18.6
19.0 14.1 15.8 12.9 preferably >30% Tensile Strength (MPa)
>25 MPa, 50 40 34 37 33 35 40 preferably >40 MPa Young's
Modulus (MPa) >900 MPa, 1350 1248 995 1171 917 1035 1260
preferably >1100 MPa
These results showed that compositions P25, P27, and P29 had
desirable stress relaxation of the initial load. P25 had the
highest level of reactive diluent from the group of P23-P27. While
P28 had a comparable level of reactive diluent to P25, the change
of crosslinker from TGM1-RD1 to TGM1-D4MA resulted in decreased
stress relaxation of initial load as well as elongation at break.
Of these compositions, only P23 provided a desirable elongation at
break value. Additional compositions were created to analyze
changes to the stress relaxation of the initial load, with respect
to alterations to glass transition modifiers and using a various
toughness modifier. The following components were mixed in the
proportions shown in Table 30 to give curable compositions (30) to
(33):
TABLE-US-00030 TABLE 30 Compositions (30) to (33) Toughness
Reactive Reactive Crosslinker.sup.1 Crosslinker.sup.2
modifier.sup.3 Diluent.sup.4 Diluent.- sup.5 Additive.sup.6 Comp.
No. (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) 30 10 20 45 25 -- --
31 14.3 -- 43 -- 38 4.8 32 27.9 -- 34.6 -- 33.5 4 33 17.9 -- 39
38.1 -- 5 .sup.1TGM1-D4MA (TGM1 with 15 wt % D4MA); .sup.2H1188;
.sup.3TNM2_D3MA; .sup.4HSMA; .sup.5BSMA; .sup.6SIU2400
SIU2400 is a functionalized silicone urethane acrylate having 10
functional groups, diluted with 10 wt % TPGDA (tripropylene glycol
diacrylate). Prior to curing, to each of these compositions was
added TPO-L as a photoinitiator (1 wt %). The following Table 31
provides relevant properties of the crosslinked polymers obtained
from curable compositions (30) to (33) using Hot Lithography.
TABLE-US-00031 TABLE 31 Results of Compositions 30 to 33 Desirable
Property Range P30 P31 P32 P33 Stress Relaxation of >20%, 21.67
16.84 12.31 13.51 Initial Load (%) preferably >35% Elongation at
>20%, 21.0 21.4 15.2 25.8 Break (%) preferably >30% Tensile
Strength >25 MPa, 40 45 40 39 (MPa) preferably >40 MPa
Young's Modulus >900 MPa, 997 1003 1109 879 (MPa) preferably
>1100 MPa
Overall, these results show that various combinations of
cross-linkers and toughness modifiers can provide desirable cured
compositions having stress relaxation over 20% of the initial load.
Of the combinations, P30 had both a desirable stress relaxation of
initial load, and elongation at break. These data indicate the
addition of multifunctional additives (compositions 26-27 and
31-33) may decrease the value of the stress relaxation of initial
load.
Example 12: Preparation of Curable Compositions (34) to (35)
Compositions 26 and 27 were prepared as described above. The
following components were mixed in the proportions shown in Table
32 to give curable compositions (34) to (35):
TABLE-US-00032 TABLE 32 Compositions (26-27) and (34-35) Reac-
Reac- Toughness tive tive Addi- Addi- Comp. Crosslinker.sup.1
modifier.sup.2 Diluent.sup.3 Diluent.sup.4 tive.su- p.5 tive.sup.6
No. (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) 26 14.2 43 38 -- --
4.8 34 14.2 43 -- 38 4.8 -- 27 12 45 38 -- -- 5 35 15 45 40 -- --
-- .sup.1TGM1-RD1 (TGM1 with 15 wt % RD1); .sup.2TNM2_RD1 (TNM2
with 30 wt % RD1); .sup.3HSMA; .sup.4BSMA; .sup.5SIU2400;
.sup.6BDT1006
To each of these compositions was added TPO-L as a photoinitiator
(1 wt %). To P26, P27, P34, and P35 was added 0.25, 0.2, 0.25, and
0.3 wt % 2,2'-dihydroxy-4-methoxybenzophenone, respectively, as a
UV-blocker. The following Table 33 provides relevant properties of
the crosslinked polymers obtained from curable compositions (26-27)
and (34-35) using Hot Lithography.
TABLE-US-00033 TABLE 33 Results of Compositions 26-27 and 34-35
Property P26 P27 P34 P35 Elongation at Break (%) 19.0 14.1 16.4
22.6 (average) Tensile Strength (MPa) 37 33 35 35 (average) Young's
Modulus (MPa) 1171 917 932 1056
These results provide a comparison of composition having no
additive (composition P35) to similar compositions having BDT1006
added to them (P26 and P27). The additive-free P35 had a longer
average elongation at break, but comparable average tensile
strength and Young's Modulus values. Composition P34 uses a
different diluent and multifunctional additive (SIU2400), and has
average values that fall near those of P26 and P27. Accordingly,
the addition of multifunctionalized additives may decrease average
elongation at break.
Example 13: Preparation of Curable Compositions (36) to (44)
The following components were mixed in the proportions shown in
Table 34 to give curable compositions (36) to (44):
TABLE-US-00034 TABLE 34 Compositions (36) to (44) Toughness
Toughness Toughness Reactive Crosslinker.sup.1 modifier.sup.2
modifier.sup.3 modifier.sup.4 Diluent.su- p.5 Additive.sup.6 Comp.
No. (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) 36 15 -- -- 45 40 --
37 25 -- -- 35 40 -- 38 35 -- -- 35 30 -- 39 25 -- -- 45 30 -- 40
20 45 -- -- 35 30 41 40 -- -- -- 30 30 42 25 -- 35 -- 30 10 43 15
45 -- -- 40 -- 44 14.3 43 -- -- 38 4.8 .sup.1TGM1-D3MA (TGM1 with
15 wt % D3MA); .sup.2TNM2_RD1, 16 kDa; .sup.3TNM2_RD1, 25 kDa;
.sup.4UA5216, separated; .sup.5HSMA; .sup.6SIU2400
UA5216 refers to Miramer UA5216, an aliphatic difunctional
acrylate. Other aliphatic difunctional acrylates are envisioned to
have similar effects. To each of these compositions was added TPO-L
as a photoinitiator (1 wt %). To P36 and P37 was added 0.2 and 0.19
wt % 2,2'-dihydroxy-4-methoxybenzophenone, respectively, as a
UV-blocker. The following Table 35 provides relevant properties of
the crosslinked polymers obtained from curable compositions (36) to
(44) using Hot Lithography.
TABLE-US-00035 TABLE 35 Results of Compositions 36 to 44 Property
P36 P37 P38 P39 P40 P41 P42 P43 P44 Elongation at Break (%) 92.5
29.0 24.6 55.7 29.5 5.1 18.6 32.4 45.3 (average) Tensile Strength
(MPa) 25 39 45 33 36 44 44 34 33 (average) Young's Modulus (MPa)
370 734 737 474 544 -- -- -- --
These results provide data allowing for assorted comparisons.
Numerous compositions had preferable levels of elongation at break,
with P36 having a very high value of 92.5%, and P39, P43, and P44
all being over 30%. The decrease of toughness modifier and increase
of crosslinker between P36 and P37 sharply decreased the average
elongation at break while increasing average tensile strength and
Young's Modulus. Similar effects were observed between the decrease
of toughness modifier and increase of crosslinker between P39 and
P38. A comparison of P42 and P37 provides information relating to
importance the toughness modifier can play, with observable
differences in average elongation at break, average tensile
strength, and average Young's Modulus between P39 (using UA5216 as
the toughness modifier) and P42 (using TNM2_RD2, 25 kDa as the
toughness modifier).
Example 14: Preparation of Curable Compositions (45) to (51)
The following components were mixed in the proportions shown in
Table 36 to give curable compositions (45) to (51):
TABLE-US-00036 TABLE 36 Compositions (45) to (51) Reac- Reac-
Toughness tive tive Addi- Addi- Comp. Crosslinker.sup.1
modifier.sup.2 Diluent.sup.3 Diluent.sup.4 tive.su- p.5 tive.sup.6
No. (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) 45 20 31.5 35 13.5 --
-- 46 20 45 35 -- -- 0.6 47 25 35 40 -- -- 0.6 48 20 31.5 35 13.5
-- 0.4 49 20 31.5 35 13.5 -- 1 50 25 24.5 40 10.5 -- 1 51 14.3 30
38 12.9 4.8 -- .sup.1TGM1-RD1 (MUA + 30); .sup.2TNM2_RD1 (2098-5B);
.sup.3HSMA; .sup.4triethylene glycol dimethacrylate; .sup.5SIU2400;
.sup.6TPO-L
The photoinitiator TPO-L was added following the initial mixture of
proportions from the other columns in Table 36. The following Table
37 provides relevant properties of the crosslinked polymers
obtained from curable compositions (45) to (51) using Hot
Lithography.
TABLE-US-00037 TABLE 37 Results of Compositions 45 to 51 Property
P45 P46 P47 P48 P49 P50 P51 Elongation at Break (%) 24.9 113.9 59.5
40.7 36.9 20.5 9.9 (average) Tensile Strength (MPa) 41 42 44 46 44
50 55 (average) Young's Modulus (MPa) 1214 572 1007 1059 1134 1540
1900 Average Yield Strength 41 23 35 40 39 51 60 (MPa)
Table 37 shows that compositions P47-P51 each had a desirable
tensile strength at yield (over 25 MPa), while compositions P50 and
P51 had tensile strengths at yield in the preferred range (over 40
MPa). Conversely, P50 and P51 had the lowest average elongation at
break values of the table, while P45-P49 each had elongation at
break values in the desired range (greater than 20%), and P46-P49
were also in the preferred range (greater than 30%). P46 had the
highest elongation at break value and the lowest average yield
strength, while P51 had the highest average yield strength and the
lowest average elongation at break of the tabled compositions.
While P45 did not include any photoinitiator, P48 used 0.4 wt %
while P49 used 1 wt %. A comparison of P45 to P48 and P49 shows
that the addition of at least some photoinitiator increases the
average elongation at break, increases the tensile strength, and
slightly decreases the Young's Modulus.
Example 15: Preparation of Curable Compositions (52) to (56) with
Defoamers
Composition 23 was prepared as discussed previously. The following
components were mixed in the proportions shown in Table 38 to give
curable compositions (52) to (56), with various defoamers:
TABLE-US-00038 TABLE 38 Compositions (52) to (56) Toughness
Reactive Comp. Crosslinker.sup.1 modifier.sup.2 Diluent.sup.3 No.
(wt %) (wt %) (wt %) Defoamer 23 45 45 10 -- 52 45 45 10 BYK
.RTM.7420ET 53 45 45 10 BYK .RTM.7411ES 54 45 45 10 BYK .RTM.7410ET
55 45 45 10 TEGO .RTM. RAD2100 56 45 45 10 TEGO .RTM. WET510
.sup.1TGM1-RD1 (TGM1 with 30 wt % TEGDMA); .sup.2TNM2_RD1 (16 kDa);
.sup.3HSMA
Following formation of the initial mixture comprising the
cross-linker, the toughness modifier, and the reactive diluent, 1
wt % of the defoamer was added to each of the corresponding samples
52-56. To each of these compositions was added TPO-L as a
photoinitiator (1 wt %). To P52-P56 was added 0.1 wt %
2,2'-dihydroxy-4-methoxybenzophenone as a UV-blocker. To P23 was
added 0.2 wt % 2,2'-dihydroxy-4-methoxybenzophenone as a
UV-blocker. The following Table 39 provides relevant properties of
the crosslinked polymers obtained from curable compositions (23)
and (52) to (56) using Hot Lithography.
TABLE-US-00039 TABLE 39 Results of Compositions 23 and 52 to 56
Property P23 P52 P53 P54 P55 P56 Elongation at 20.5 25.5 25.6 23.3
27.4 22.8 Break (%) (average) Tensile 50 49 49 49 51 45 Strength
(MPa) (average) Young's 1350 1136 1136 1156 1128 1145 Modulus
(MPa)
Table 39 indicates the addition of a foaming agent to the
composition can increase the average elongation at break value, to
varying degrees. Changes in tensile strength values were moderate
in most cases, though the defoaming agent TEGO.RTM. WET510
moderately decreased the tensile strength of composition P56. The
addition of defoaming agents to the compositions appears to
moderately decrease the value of the Young's Modulus.
Example 16: Preparation of Curable Compositions (57) to (59)
The following components were mixed in the proportions shown in
Table 40 to give curable compositions (57) to (59)
TABLE-US-00040 TABLE 40 Compositions (57) to (59) Toughness
Reactive Reactive Comp. Crosslinker.sup.1 Crosslinker.sup.2
modifier.sup.3 Diluent.sup.4 Dil- uent.sup.5 No. (wt %) (wt %) (wt
%) (wt %) (wt %) 57 -- 30 45 25 -- 58 -- 30 45 -- 25 59 30 -- 45 --
25 .sup.1LPU624; .sup.2TGM1-D3MA (TGM1 with 15 wt % D3MA);
.sup.3TNM2_RD1 (16 kDa); .sup.4HSMA; .sup.5BSMA
Following formation of the initial mixture comprising the
cross-linker, the toughness modifier, and the reactive diluent,
TPO-L was added as a photoinitiator (1 wt %) to each sample. To
P57-P58 was added 0.15 wt % 2,2'-dihydroxy-4-methoxybenzophenone as
a UV-blocker. To P59 was added 0.225 wt %
2,2'-dihydroxy-4-methoxybenzophenone as a UV-blocker. The following
Table 41 provides relevant properties of the crosslinked polymers
obtained from curable compositions (57) to (59) using Hot
Lithography.
TABLE-US-00041 TABLE 41 Results of Compositions 57 to 59 Property
P57 P58 P59 Elongation at Break (%) 33.4 13.7 24.8 (average)
Tensile Strength (MPa) 43 32 38 (average) Young's Modulus (MPa)
1388 1289 1529
These results provide data allowing for assorted comparisons of
compositions. P57 uses HSMA as diluent, while P58 uses BSMA as
diluent. The shift from HSMA to BSMA caused a minor decrease in the
Young's Modulus. However, substitution of LPU624 as cross-linker in
P59 led to a moderate increase in Young's Modulus, when compared
with P58.
Example 17: Preparation of Curable Compositions (60) to (61)
The following components were mixed in the proportions shown in
Table 42 to give curable compositions (60) to (61):
TABLE-US-00042 TABLE 42 Compositions (60) to (61) Toughness
Reactive Comp. modifier.sup.1 Diluent.sup.2 Additive.sup.3 No. (wt
%) (wt %) (wt %) 60 30 70 0.6 61 30 70 3 .sup.1TNM2_RD1 (TMX);
.sup.2HSMA; .sup.3TPO-L
Following formation of the initial mixtures comprising the
toughness modifier and the reactive diluent, TPO-L was added as a
photoinitiator to each sample, as provided by Table 42. To P60-P61
was added 0.15 wt % 2,2'-dihydroxy-4-methoxybenzophenone as a
UV-blocker. The following Table 43 provides relevant properties of
the crosslinked polymers obtained from curable compositions (60) to
(61) using Hot Lithography.
TABLE-US-00043 TABLE 43 Results of Compositions 60 to 61 Property
P60 P61 Elongation at Break (%) 50.6 19.9 (average) Tensile
Strength (MPa) 25 26 (average) Young's Modulus (MPa) 815 1168
Average Yield Strength 15 16 (MPa)
These results provide data assessing the effect the amount of
photoinitiator can have on a composition. Both P60 and P61 were
generated using equivalent amounts of TNM2_RD1 as a toughness
modifier, and HSMA as a reactive diluent. However, P61 had 5-fold
the amount of TPO-L photoinitiator. As a result, P61 had a
substantially decreased elongation at break value, and a
substantially increased Young's Modulus. This result provides
further verification from Example 10 (comparison of P16 to P17 and
P18 to P19) that higher levels of a photoinitiator additive can
decrease the average elongation at break. The changes in tensile
strength and average yield strength were moderate.
Example 18: Printing Using Compositions Disclosed Above
Structures were printed using compositions, which were generated as
specified above. The printing study assessed the percent laser
power (375 nm UV radiation from a diode laser from Soliton, having
an output power of 2.times.70 mW) used to cure compositions, the
scan speed assessed, the number of repetitions that were stacked,
the temperature of the curing, the hatching, as well as the resin
height. These values are provided below in Table 44:
TABLE-US-00044 TABLE 44 Printing Results of Select Compositions
Laser Scan Temper- Resin Comp. Power Speed Repetition ature Height
No. (%) (m/s) (#) (.degree. C.) Hatching (mm) 23 60 2 1 100 xy 0.4
24 100 2 1 90 xy -- 25 100 2 1 90 xy 0.4 26 100 8 -- 90 x 0.3 27
100 2 1 100 xy 0.4 28 50 2 1 90 xy 0.4 29 60 2 1 100 xy 0.4 30 60 2
1 100 xy 0.4 35 100 4 10 90 x 0.3 36 100 0.5 1 100 xy -- 45 100 8
10 70 x -- 47 100 8 10 90 x -- 57 100 0.5 1 100 xy -- 58 100 0.5 1
100 xy -- 59 100 0.5 1 100 xy -- 60 100 8 12 80 x -- 61 100 8 12 80
x --
These data show that many variations of the disclosed compositions
could be used in a printable format. A comparison of compound P25
to P26 shows the benefits of adding a multifunctionalized agent.
Composition P26 is similar to P25, but to it was added BDT1006. As
a result, the composition P26 could be printed at a faster rate,
though the resin height did appear to drop slightly. Table 44 shows
that various blends of crosslinkers, toughness modifiers, reactive
diluents, and additives as described herein can be applied toward
3D printable materials and structures.
The terms and expressions which have been employed herein are used
as terms of description and not of limitation, and there is no
intention in the use of such terms and expressions of excluding any
equivalents of the features shown and described or portions
thereof, but it is recognized that various modifications are
possible within the scope of the invention claimed. Thus, it should
be understood that although the present invention has been
specifically disclosed by preferred embodiments, exemplary
embodiments and optional features, modification and variation of
the concepts herein disclosed may be resorted to by those skilled
in the art, and that such modifications and variations are
considered to be within the scope of this invention as defined by
the appended claims. The specific embodiments provided herein are
examples of useful embodiments of the present invention and it will
be apparent to one skilled in the art that the present invention
may be carried out using a large number of variations of the
devices, device components, methods steps set forth in the present
description. As will be obvious to one of skill in the art, methods
and devices useful for the present methods can include a large
number of optional composition and processing elements and
steps.
When a group of substituents is disclosed herein, it is understood
that all individual members of that group and all subgroups,
including any isomers, enantiomers, and diastereomers of the group
members, are disclosed separately. When a Markush group or other
grouping is used herein, all individual members of the group and
all combinations and subcombinations possible of the group are
intended to be individually included in the disclosure. When a
compound is described herein such that a particular isomer,
enantiomer or diastereomer of the compound is not specified, for
example, in a formula or in a chemical name, that description is
intended to include each isomers and enantiomer of the compound
described individual or in any combination. Additionally, unless
otherwise specified, all isotopic variants of compounds disclosed
herein are intended to be encompassed by the disclosure. Specific
names of compounds are intended to be exemplary, as it is known
that one of ordinary skill in the art can name the same compounds
differently.
It must be noted that as used herein and in the appended claims,
the singular forms "a", "an", and "the" include plural reference
unless the context clearly dictates otherwise. Thus, for example,
reference to "a cell" includes a plurality of such cells and
equivalents thereof known to those skilled in the art, and so
forth. As well, the terms "a" (or "an"), "one or more" and "at
least one" can be used interchangeably herein. It is also to be
noted that the terms "comprising", "including", and "having" can be
used interchangeably.
Unless defined otherwise, all technical and scientific terms used
herein have the same meanings as commonly understood by one of
ordinary skill in the art to which this invention belongs. Although
any methods and materials similar or equivalent to those described
herein can be used in the practice or testing of the present
invention, the preferred methods and materials are now described.
Nothing herein is to be construed as an admission that the
invention is not entitled to antedate such disclosure by virtue of
prior invention.
Every formulation or combination of components described or
exemplified herein can be used to practice the invention, unless
otherwise stated.
Whenever a range is given in the specification, for example, a
temperature range, a time range, or a composition or concentration
range, all intermediate ranges and subranges, as well as all
individual values included in the ranges given are intended to be
included in the disclosure. As used herein, ranges specifically
include the values provided as endpoint values of the range. For
example, a range of 1 to 100 specifically includes the end point
values of 1 and 100. It will be understood that any subranges or
individual values in a range or subrange that are included in the
description herein can be excluded from the claims herein.
As used herein, "comprising" is synonymous with "including,"
"containing," or "characterized by," and is inclusive or open-ended
and does not exclude additional, unrecited elements or method
steps. As used herein, "consisting of" excludes any element, step,
or ingredient not specified in the claim element. As used herein,
"consisting essentially of" does not exclude materials or steps
that do not materially affect the basic and novel characteristics
of the claim. In each instance herein any of the terms
"comprising", "consisting essentially of" and "consisting of" may
be replaced with either of the other two terms. The invention
illustratively described herein suitably may be practiced in the
absence of any element or elements, limitation or limitations which
is not specifically disclosed herein.
One of ordinary skill in the art will appreciate that starting
materials, biological materials, reagents, synthetic methods,
purification methods, analytical methods, assay methods, and
biological methods other than those specifically exemplified can be
employed in the practice of the invention without resort to undue
experimentation. All art-known functional equivalents, of any such
materials and methods are intended to be included in this
invention. The terms and expressions which have been employed are
used as terms of description and not of limitation, and there is no
intention that in the use of such terms and expressions of
excluding any equivalents of the features shown and described or
portions thereof, but it is recognized that various modifications
are possible within the scope of the invention claimed. Thus, it
should be understood that although the present invention has been
specifically disclosed by preferred embodiments and optional
features, modification and variation of the concepts herein
disclosed may be resorted to by those skilled in the art, and that
such modifications and variations are considered to be within the
scope of this invention as defined by the appended claims.
Statements Regarding Chemical Compounds and Nomenclature
As used herein, the term "group" may refer to a functional group of
a chemical compound. Groups of the present compounds refer to an
atom or a collection of atoms that are a part of the compound.
Groups of the present invention may be attached to other atoms of
the compound via one or more covalent bonds. Groups may also be
characterized with respect to their valence state. The present
invention includes groups characterized as monovalent, divalent,
trivalent, etc. valence states.
As used herein, the term "substituted" refers to a compound wherein
a hydrogen is replaced by another functional group.
Alkyl groups include straight-chain, branched and cyclic alkyl
groups. Alkyl groups include those having from 1 to 30 carbon
atoms. Alkyl groups include small alkyl groups having 1 to 3 carbon
atoms. Alkyl groups include medium length alkyl groups having from
4-10 carbon atoms. Alkyl groups include long alkyl groups having
more than 10 carbon atoms, particularly those having 10-30 carbon
atoms. The term cycloalkyl specifically refers to an alky group
having a ring structure such as ring structure comprising 3-30
carbon atoms, optionally 3-20 carbon atoms and optionally 3-10
carbon atoms, including an alkyl group having one or more rings.
Cycloalkyl groups include those having a 3-, 4-, 5-, 6-, 7-, 8-, 9-
or 10-member carbon ring(s) and particularly those having a 3-, 4-,
5-, 6-, 7- or 8-member ring(s). The carbon rings in cycloalkyl
groups can also carry alkyl groups. Cycloalkyl groups can include
bicyclic and tricyclic alkyl groups. Alkyl groups are optionally
substituted. Substituted alkyl groups include among others those
which are substituted with aryl groups, which in turn can be
optionally substituted. Specific alkyl groups include methyl,
ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, s-butyl,
t-butyl, cyclobutyl, n-pentyl, branched-pentyl, cyclopentyl,
n-hexyl, branched hexyl, and cyclohexyl groups, all of which are
optionally substituted. Substituted alkyl groups include fully
halogenated or semihalogenated alkyl groups, such as alkyl groups
having one or more hydrogens replaced with one or more fluorine
atoms, chlorine atoms, bromine atoms and/or iodine atoms.
Substituted alkyl groups include fully fluorinated or
semifluorinated alkyl groups, such as alkyl groups having one or
more hydrogens replaced with one or more fluorine atoms. An alkoxy
group is an alkyl group that has been modified by linkage to oxygen
and can be represented by the formula R--O and can also be referred
to as an alkyl ether group. Examples of alkoxy groups include, but
are not limited to, methoxy, ethoxy, propoxy, butoxy and heptoxy.
Alkoxy groups include substituted alkoxy groups wherein the alky
portion of the groups is substituted as provided herein in
connection with the description of alkyl groups. As used herein
MeO-- refers to CH.sub.3O--.
Alkenyl groups include straight-chain, branched and cyclic alkenyl
groups. Alkenyl groups include those having 1, 2 or more double
bonds and those in which two or more of the double bonds are
conjugated double bonds. Alkenyl groups include those having from 2
to 20 carbon atoms. Alkenyl groups include small alkenyl groups
having 2 to 3 carbon atoms. Alkenyl groups include medium length
alkenyl groups having from 4-10 carbon atoms. Alkenyl groups
include long alkenyl groups having more than 10 carbon atoms,
particularly those having 10-20 carbon atoms. Cycloalkenyl groups
include those in which a double bond is in the ring or in an
alkenyl group attached to a ring. The term cycloalkenyl
specifically refers to an alkenyl group having a ring structure,
including an alkenyl group having a 3-, 4-, 5-, 6-, 7-, 8-, 9- or
10-member carbon ring(s) and particularly those having a 3-, 4-,
5-, 6-, 7- or 8-member ring(s). The carbon rings in cycloalkenyl
groups can also carry alkyl groups. Cycloalkenyl groups can include
bicyclic and tricyclic alkenyl groups. Alkenyl groups are
optionally substituted. Substituted alkenyl groups include among
others those that are substituted with alkyl or aryl groups, which
groups in turn can be optionally substituted. Specific alkenyl
groups include ethenyl, prop-1-enyl, prop-2-enyl, cycloprop-1-enyl,
but-1-enyl, but-2-enyl, cyclobut-1-enyl, cyclobut-2-enyl,
pent-1-enyl, pent-2-enyl, branched pentenyl, cyclopent-1-enyl,
hex-1-enyl, branched hexenyl, cyclohexenyl, all of which are
optionally substituted. Substituted alkenyl groups include fully
halogenated or semihalogenated alkenyl groups, such as alkenyl
groups having one or more hydrogens replaced with one or more
fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
Substituted alkenyl groups include fully fluorinated or
semifluorinated alkenyl groups, such as alkenyl groups having one
or more hydrogen atoms replaced with one or more fluorine
atoms.
Aryl groups include groups having one or more 5-, 6-, 7- or
8-member aromatic rings, including heterocyclic aromatic rings. The
term heteroaryl specifically refers to aryl groups having at least
one 5-, 6-, 7- or 8-member heterocyclic aromatic rings. Aryl groups
can contain one or more fused aromatic rings, including one or more
fused heteroaromatic rings, and/or a combination of one or more
aromatic rings and one or more nonaromatic rings that may be fused
or linked via covalent bonds. Heterocyclic aromatic rings can
include one or more N, O, or S atoms in the ring. Heterocyclic
aromatic rings can include those with one, two or three N atoms,
those with one or two O atoms, and those with one or two S atoms,
or combinations of one or two or three N, O or S atoms. Aryl groups
are optionally substituted. Substituted aryl groups include among
others those that are substituted with alkyl or alkenyl groups,
which groups in turn can be optionally substituted. Specific aryl
groups include phenyl, biphenyl groups, pyrrolidinyl,
imidazolidinyl, tetrahydrofuryl, tetrahydrothienyl, furyl, thienyl,
pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, indolyl,
imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridinyl,
benzoxadiazolyl, benzothiadiazolyl, and naphthyl groups, all of
which are optionally substituted. Substituted aryl groups include
fully halogenated or semihalogenated aryl groups, such as aryl
groups having one or more hydrogens replaced with one or more
fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
Substituted aryl groups include fully fluorinated or
semifluorinated aryl groups, such as aryl groups having one or more
hydrogens replaced with one or more fluorine atoms. Aryl groups
include, but are not limited to, aromatic group-containing or
heterocylic aromatic group-containing groups corresponding to any
one of the following: benzene, naphthalene, naphthoquinone,
diphenylmethane, fluorene, anthracene, anthraquinone, phenanthrene,
tetracene, tetracenedione, pyridine, quinoline, isoquinoline,
indoles, isoindole, pyrrole, imidazole, oxazole, thiazole,
pyrazole, pyrazine, pyrimidine, purine, benzimidazole, furans,
benzofuran, dibenzofuran, carbazole, acridine, acridone,
phenanthridine, thiophene, benzothiophene, dibenzothiophene,
xanthene, xanthone, flavone, coumarin, azulene or anthracycline. As
used herein, a group corresponding to the groups listed above
expressly includes an aromatic or heterocyclic aromatic group,
including monovalent, divalent and polyvalent groups, of the
aromatic and heterocyclic aromatic groups listed herein provided in
a covalently bonded configuration in the compounds of the invention
at any suitable point of attachment. In embodiments, aryl groups
contain between 5 and 30 carbon atoms. In embodiments, aryl groups
contain one aromatic or heteroaromatic six-member ring and one or
more additional five- or six-member aromatic or heteroaromatic
ring. In embodiments, aryl groups contain between five and eighteen
carbon atoms in the rings. Aryl groups optionally have one or more
aromatic rings or heterocyclic aromatic rings having one or more
electron donating groups, electron withdrawing groups and/or
targeting ligands provided as substituents.
Arylalkyl groups are alkyl groups substituted with one or more aryl
groups wherein the alkyl groups optionally carry additional
substituents and the aryl groups are optionally substituted.
Specific alkylaryl groups are phenyl-substituted alkyl groups,
e.g., phenylmethyl groups. Alkylaryl groups are alternatively
described as aryl groups substituted with one or more alkyl groups
wherein the alkyl groups optionally carry additional substituents
and the aryl groups are optionally substituted. Specific alkylaryl
groups are alkyl-substituted phenyl groups such as methylphenyl.
Substituted arylalkyl groups include fully halogenated or
semihalogenated arylalkyl groups, such as arylalkyl groups having
one or more alkyl and/or aryl groups having one or more hydrogens
replaced with one or more fluorine atoms, chlorine atoms, bromine
atoms and/or iodine atoms.
As used herein, the terms "alkylene" and "alkylene group" are used
synonymously and refer to a divalent group derived from an alkyl
group as defined herein. The invention includes compounds having
one or more alkylene groups. Alkylene groups in some compounds
function as attaching and/or spacer groups. Compounds of the
invention may have substituted and/or unsubstituted
C.sub.1-C.sub.20 alkylene, C.sub.1-C.sub.10 alkylene and
C.sub.1-C.sub.5 alkylene groups.
As used herein, the terms "cycloalkylene" and "cycloalkylene group"
are used synonymously and refer to a divalent group derived from a
cycloalkyl group as defined herein. The invention includes
compounds having one or more cycloalkylene groups. Cycloalkyl
groups in some compounds function as attaching and/or spacer
groups. Compounds of the invention may have substituted and/or
unsubstituted C.sub.3-C.sub.20 cycloalkylene, C.sub.3-C.sub.10
cycloalkylene and C.sub.3-C.sub.5 cycloalkylene groups.
As used herein, the terms "arylene" and "arylene group" are used
synonymously and refer to a divalent group derived from an aryl
group as defined herein. The invention includes compounds having
one or more arylene groups. In some embodiments, an arylene is a
divalent group derived from an aryl group by removal of hydrogen
atoms from two intra-ring carbon atoms of an aromatic ring of the
aryl group. Arylene groups in some compounds function as attaching
and/or spacer groups. Arylene groups in some compounds function as
chromophore, fluorophore, aromatic antenna, dye and/or imaging
groups. Compounds of the invention include substituted and/or
unsubstituted C.sub.3-C.sub.30 arylene, C.sub.3-C.sub.20 arylene,
C.sub.3-C.sub.10 arylene and C.sub.1-C.sub.5 arylene groups.
As used herein, the terms "heteroarylene" and "heteroarylene group"
are used synonymously and refer to a divalent group derived from a
heteroaryl group as defined herein. The invention includes
compounds having one or more heteroarylene groups. In some
embodiments, a heteroarylene is a divalent group derived from a
heteroaryl group by removal of hydrogen atoms from two intra-ring
carbon atoms or intra-ring nitrogen atoms of a heteroaromatic or
aromatic ring of the heteroaryl group. Heteroarylene groups in some
compounds function as attaching and/or spacer groups. Heteroarylene
groups in some compounds function as chromophore, aromatic antenna,
fluorophore, dye and/or imaging groups. Compounds of the invention
include substituted and/or unsubstituted C.sub.3-C.sub.30
heteroarylene, C.sub.3-C.sub.20 heteroarylene, C.sub.1-C.sub.10
heteroarylene and C.sub.3-C.sub.5 heteroarylene groups.
As used herein, the terms "alkenylene" and "alkenylene group" are
used synonymously and refer to a divalent group derived from an
alkenyl group as defined herein. The invention includes compounds
having one or more alkenylene groups. Alkenylene groups in some
compounds function as attaching and/or spacer groups. Compounds of
the invention include substituted and/or unsubstituted
C.sub.2-C.sub.20 alkenylene, C.sub.2-C.sub.10 alkenylene and
C.sub.2-C.sub.5 alkenylene groups.
As used herein, the terms "cylcoalkenylene" and "cylcoalkenylene
group" are used synonymously and refer to a divalent group derived
from a cylcoalkenyl group as defined herein. The invention includes
compounds having one or more cylcoalkenylene groups.
Cycloalkenylene groups in some compounds function as attaching
and/or spacer groups. Compounds of the invention include
substituted and/or unsubstituted C.sub.3-C.sub.20 cylcoalkenylene,
C.sub.3-C.sub.10 cylcoalkenylene and C.sub.3-C.sub.5
cylcoalkenylene groups.
As used herein, the terms "alkynylene" and "alkynylene group" are
used synonymously and refer to a divalent group derived from an
alkynyl group as defined herein. The invention includes compounds
having one or more alkynylene groups. Alkynylene groups in some
compounds function as attaching and/or spacer groups. Compounds of
the invention include substituted and/or unsubstituted
C.sub.2-C.sub.20 alkynylene, C.sub.2-C.sub.10 alkynylene and
C.sub.2-C.sub.5 alkynylene groups.
As used herein, the term "halo" refers to a halogen group such as a
fluoro (--F), chloro (--Cl), bromo (--Br) or iodo (--I)
The term "heterocyclic" refers to ring structures containing at
least one other kind of atom, in addition to carbon, in the ring.
Examples of such heteroatoms include nitrogen, oxygen and sulfur.
Heterocyclic rings include heterocyclic alicyclic rings and
heterocyclic aromatic rings. Examples of heterocyclic rings
include, but are not limited to, pyrrolidinyl, piperidyl,
imidazolidinyl, tetrahydrofuryl, tetrahydrothienyl, furyl, thienyl,
pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, indolyl,
imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridinyl,
benzoxadiazolyl, benzothiadiazolyl, triazolyl and tetrazolyl
groups. Atoms of heterocyclic rings can be bonded to a wide range
of other atoms and functional groups, for example, provided as
substituents.
The term "carbocyclic" refers to ring structures containing only
carbon atoms in the ring. Carbon atoms of carbocyclic rings can be
bonded to a wide range of other atoms and functional groups, for
example, provided as substituents.
The term "alicyclic ring" refers to a ring, or plurality of fused
rings, that is not an aromatic ring. Alicyclic rings include both
carbocyclic and heterocyclic rings.
The term "aromatic ring" refers to a ring, or a plurality of fused
rings, that includes at least one aromatic ring group. The term
aromatic ring includes aromatic rings comprising carbon, hydrogen
and heteroatoms. Aromatic ring includes carbocyclic and
heterocyclic aromatic rings. Aromatic rings are components of aryl
groups.
The term "fused ring" or "fused ring structure" refers to a
plurality of alicyclic and/or aromatic rings provided in a fused
ring configuration, such as fused rings that share at least two
intra ring carbon atoms and/or heteroatoms.
As used herein, the term "alkoxyalkyl" refers to a substituent of
the formula alkyl-O-alkyl.
As used herein, the term "polyhydroxyalkyl" refers to a substituent
having from 2 to 12 carbon atoms and from 2 to 5 hydroxyl groups,
such as the 2,3-dihydroxypropyl, 2,3,4-trihydroxybutyl or
2,3,4,5-tetrahydroxypentyl residue.
As used herein, the term "polyalkoxyalkyl" refers to a substituent
of the formula alkyl-(alkoxy)n-alkoxy wherein n is an integer from
1 to 10, preferably 1 to 4, and more preferably for some
embodiments 1 to 3.
As to any of the groups described herein that contain one or more
substituents, it is understood that such groups do not contain any
substitution or substitution patterns which are sterically
impractical and/or synthetically non-feasible. In addition, the
compounds of this invention include all stereochemical isomers
arising from the substitution of these compounds. Optional
substitution of alkyl groups includes substitution with one or more
alkenyl groups, aryl groups or both, wherein the alkenyl groups or
aryl groups are optionally substituted. Optional substitution of
alkenyl groups includes substitution with one or more alkyl groups,
aryl groups, or both, wherein the alkyl groups or aryl groups are
optionally substituted. Optional substitution of aryl groups
includes substitution of the aryl ring with one or more alkyl
groups, alkenyl groups, or both, wherein the alkyl groups or
alkenyl groups are optionally substituted.
Optional substituents for any alkyl, alkenyl and aryl group
includes substitution with one or more of the following
substituents, among others:
halogen, including fluorine, chlorine, bromine or iodine;
pseudohalides, including --CN, --OCN (cyanate), --NCO (isocyanate),
--SCN (thiocyanate) and --NCS (isothiocyanate);
--COOR, where R is a hydrogen or an alkyl group or an aryl group
and more specifically where R is a methyl, ethyl, propyl, butyl, or
phenyl group all of which groups are optionally substituted;
--COR, where R is a hydrogen or an alkyl group or an aryl group and
more specifically where R is a methyl, ethyl, propyl, butyl, or
phenyl group all of which groups are optionally substituted;
--CON(R).sub.2, where each R, independently of each other R, is a
hydrogen or an alkyl group or an aryl group and more specifically
where R is a methyl, ethyl, propyl, butyl, or phenyl group all of
which groups are optionally substituted; and where R and R can form
a ring which can contain one or more double bonds and can contain
one or more additional carbon atoms;
--OCON(R).sub.2, where each R, independently of each other R, is a
hydrogen or an alkyl group or an aryl group and more specifically
where R is a methyl, ethyl, propyl, butyl, or phenyl group all of
which groups are optionally substituted; and where R and R can form
a ring which can contain one or more double bonds and can contain
one or more additional carbon atoms;
--N(R).sub.2, where each R, independently of each other R, is a
hydrogen, or an alkyl group, or an acyl group or an aryl group and
more specifically where R is a methyl, ethyl, propyl, butyl, phenyl
or acetyl group, all of which are optionally substituted; and where
R and R can form a ring that can contain one or more double bonds
and can contain one or more additional carbon atoms;
--SR, where R is hydrogen or an alkyl group or an aryl group and
more specifically where R is hydrogen, methyl, ethyl, propyl,
butyl, or a phenyl group, which are optionally substituted;
--SO.sub.2R, or --SOR, where R is an alkyl group or an aryl group
and more specifically where R is a methyl, ethyl, propyl, butyl, or
phenyl group, all of which are optionally substituted;
--OCOOR, where R is an alkyl group or an aryl group;
--SO.sub.2N(R).sub.2, where each R, independently of each other R,
is a hydrogen, or an alkyl group, or an aryl group all of which are
optionally substituted and wherein R and R can form a ring that can
contain one or more double bonds and can contain one or more
additional carbon atoms; and
--OR, where R is H, an alkyl group, an aryl group, or an acyl group
all of which are optionally substituted. In a particular example R
can be an acyl yielding --OCOR'', wherein R'' is a hydrogen or an
alkyl group or an aryl group and more specifically where R'' is
methyl, ethyl, propyl, butyl, or phenyl groups all of which groups
are optionally substituted.
Specific substituted alkyl groups include haloalkyl groups,
particularly trihalomethyl groups and specifically trifluoromethyl
groups. Specific substituted aryl groups include mono-, di-, tri,
tetra- and pentahalo-substituted phenyl groups; mono-, di, tri-,
tetra-, penta-, hexa-, and hepta-halo-substituted naphthalene
groups; 3- or 4-halo-substituted phenyl groups, 3- or
4-alkyl-substituted phenyl groups, 3- or 4-alkoxy-substituted
phenyl groups, 3- or 4-RCO-substituted phenyl, 5- or
6-halo-substituted naphthalene groups. More specifically,
substituted aryl groups include acetylphenyl groups, particularly
4-acetylphenyl groups; fluorophenyl groups, particularly
3-fluorophenyl and 4-fluorophenyl groups; chlorophenyl groups,
particularly 3-chlorophenyl and 4-chlorophenyl groups; methylphenyl
groups, particularly 4-methylphenyl groups; and methoxyphenyl
groups, particularly 4-methoxyphenyl groups.
As to any of the above groups that contain one or more
substituents, it is understood that such groups do not contain any
substitution or substitution patterns which are sterically
impractical and/or synthetically non-feasible. In addition, the
compounds of this invention include all stereochemical isomers
arising from the substitution of these compounds.
* * * * *